Emulsion including polymers containing a 1,1-disubstituted alkene compound, adhesives, coatings, and methods thereof

ABSTRACT

The present teachings show that it is possible to polymerize 1,1-disubstituted alkene compounds in an emulsion (for example using a water based carrier liquid), despite the possible reactions between the monomer and water. Polymerization of 1,1-disubstituted alkene compounds in an emulsion provides opportunities to better control the polymerization compared with bulk polymerization. The emulsion polymerization techniques can be employed for preparing homopolymers, copolymers (e.g., random copolymers), and block copolymers.

CLAIM OF PRIORITY

The present application is a continuation of U.S. patent applicationSer. No. 14/966,409 filed on Dec. 11, 2105, the contents of which areincorporated herein by reference in its entirety. The presentapplication also claims priority to U.S. patent application Ser. No.14/789,178 filed on Jul. 1, 2015, and U.S. Provisional PatentApplications Nos. 62/186,479 filed on Jun. 30, 2015, 62/182,076 filed onJun. 19, 2015, 62/047,283 filed on Sep. 8, 2014, and 62/047,328 filed onSep. 8, 2014, all incorporated herein by reference in their entirety.

FIELD

The teachings herein are directed at emulsion polymers including one ormore 1,1-disubstituted alkene compounds having a hydrocarbyl groupbonded to the carbonyl groups through a direct bond or through an oxygenatom, methods for preparing the emulsion polymers, compositionsincluding the emulsion polymers, and the use of the emulsion polymers.The emulsion polymers may be homopolymers consisting essentially of(e.g., about 99 weight percent or more) or entirely of a single monomeror may be copolymers including two or more monomers (e.g., a randomcopolymer or a block copolymer having a plurality of polymer blocks).The emulsion polymerization preferably is prepared by anionicpolymerization of one or more reactive 1,1-disubstituted alkenemonomers.

BACKGROUND

Polymerization of 1,1-disubstituted alkene compounds are typicallyperformed in bulk state, and frequently in situ, such as when monomer isplaced between two substrates to be adhered. The resultingpolymerization process may be difficult to control resulting in variableperformance or mechanical properties. For example, the polymerizationprocess may be characterized by one or more spikes in temperature duringthe polymerization process, such as by an increase in temperature ofabout 15° C. or more, about 30° C. or more, or even about 45° C. or more(e.g., during a polymerization reaction). Such an increase intemperature may occur in a short time period (e.g., less than 10minutes, less than 3 minutes, or even less than 1 minute). Typically,the resulting polymer may be characterized by one or more of thefollowing: a generally high level of branching, a high polydispersityindex, a high concentration of non-polymer reaction products, agenerally high viscosity, or a generally high molecular weight. Forexample, when polymerized in bulk, the resulting polymer may have a highviscosity that makes further processing and/or handling difficult.

As used herein, bulk polymerization refers to the polymerization of apolymerizable composition including one or more monomers where theconcentration of the one or more monomers is about 80 weight percent ormore, preferably about 90 weight percent or more (e.g., about 100 weightpercent), based on the total weight of the compounds in thepolymerizable composition that are liquid at room temperature.

Polymerization of 1,1-disubstituted alkene compounds using anionicpolymerization processes are useful in the bulk polymerization of1,1-disubstituted alkene compounds and processes which can operate at ornear ambient conditions (starting conditions) have been disclosed. Suchanionic bulk polymerizations may be initiated using a wide range ofinitiators, and may even be initiated by contact with certain substratesor by UV light. However, as discussed above, the bulk polymerization maylimit the ability to control the structure of the polymer moleculesand/or to be able to easily handle the resulting polymer composition orproduct. These difficulties in bulk polymerization may be particularlypronounced when manufacturing large quantities of polymer, where heattransport issues may occur, especially when there may be shear heatgenerated by the flow of the high viscosity polymer.

Bulk polymerization of 1,1-disubstituted alkene compounds also present achallenge when attempting to control the structure of the polymer byincluding one or more comonomers. For example, the high viscosity of theintermediate polymer may present difficulties in preparing a blockcopolymer (such as by sequential addition of a first monomer systemfollowed by a second monomer system into a reaction vessel). Otherproblems may arise when attempting to control the structure of a randomcopolymer, where the reaction rates of the different monomers differ sothat the monomers are not uniformly distributed along the length of thepolymer molecular. For example, copolymers including one or more1,1-disubstituted alkene compounds prepared by bulk polymerization aretypically expected to have a generally blocky sequence distributionand/or result in polymer molecules having a broad distribution ofmonomer compositions. As used herein, a copolymer having a generallyblocky sequence distribution of monomers may be characterized as havinga blockiness index of about 0.7 or less, about 0.6 or less or about 0.5or less, or about 0.4 or less.

Although emulsion polymerization processes have been employed in freeradical polymerization process (see for example, U.S. Pat. No. 7,241,834B2) to better control the polymer architecture, such processes have notgenerally been employed in anionic polymerization. In emulsionpolymerization systems, the polymerization typically occurs in smallmicelles that are distributed throughout a carrier liquid (generallywater). An emulsifier typically separates the monomer/polymer in themicelles from the carrier liquid. However, in anionic polymerization,many monomers that are capable of polymerization via anionicpolymerization are also reactive with water. For example, a Michaeladdition reaction between 1,1-disubstituted alkene compounds and wateris a known reaction which destroys the double bond so that the monomeris no longer polymerizable using anionic polymerization across thedouble bond. As such, there is a general preference to avoid using wateror to diminish the presence of water in the reaction. Similarly, thereis a possibility of a Michael addition reaction between the1,1-disubstituted alkene compound and various surfactants. For thesereasons, emulsion polymerization of 1,1-disubstituted alkene compoundshas typically been avoided and assumed unsuitable in emulsionpolymerization.

When an emulsion polymerization system is employed with free radicalpolymerization methods, sub-ambient temperatures (e.g., less than 10°C., less than 0° C., or less than −20° C. are typically required tocontrol the reaction. As such, in emulsion polymerization systems it maybe necessary to use a carrier liquid that has a low freezing point below−5° C. (such as a mixture of water and a glycol).

Additional difficulties in polymerization of 1,1-disubstituted alkenecompounds arise from the possibility of the anionic group of the growingpolymer reacting with an acid thereby terminating the reaction.Therefore, one would avoid using an acid in polymerizing1,1-disubstituted alkene compounds using anionic polymerization.

Prior attempts at anionic polymerization emulsion processes generallyhave had one or more of the following drawbacks: (1) requirement thatthe systems have low polymer concentrations (e.g., about 2 weightpercent or less, based on the total weight of the emulsion system), (2)have resulted in a prevalence for particle aggregation (even indrop-by-drop methods), (3) have lacked reproducibility for controllingmolecular weight distribution, (4) have undesirable reactantby-products, or (5) employ a low reaction temperature.

There is a need for polymerization methods, systems, and resultingpolymer compositions or products that allow for improved control of oneor more of the following properties of a polymer containing one or more1,1-disubstituted alkene compounds: the weight average molecular weight,the number average molecular weight, the polydispersity index, thezero-shear viscosity of the polymer (e.g., at one or more temperaturesof at least about 20° C. above the melting temperature of the polymer),the viscosity of the polymer system (e.g., the bulk polymer or thepolymer emulsion) at room temperature, the sequence distribution ofmonomers in a random copolymer, or having at least two different polymerblocks covalently bonded (e.g., each containing one or more1,1-disubstituted alkene compounds). There is also a need forpolymerization process which can be scaled-up (e.g., to a reactor ofabout 20 liters or more, or having a throughput of about 10 kg ofpolymer per hour or more. There is also a need for processes that resultin an emulsion. Such emulsion may be useful for applications such aspaints, coatings, finishes, polishes, and adhesives. For example, theremay be a need for process and polymer systems that result in an emulsionhaving a controlled size of emulsion particles.

SUMMARY

One aspect of the disclosure is directed at a process comprising thesteps of: agitating a mixture including: about 25 weight percent or moreof a carrier liquid, a surfactant (e.g., an emulsifier) and one or moremonomers to form micelles of the one or more monomers in the carrierliquid, wherein the one or more monomers includes one or more1,1-disubstituted alkenes; reacting an activator with at least one ofthe monomers in the micelle for initiating the anionic polymerization ofthe one or more monomers; and anionically polymerizing the one or moremonomers to a number average molecular weight of about 700 g/mole ormore.

Another aspect of the disclosure is directed at a polymer including oneor more 1,1-disubstituted alkene monomers. The polymer may be preparedusing an emulsion polymerization reaction, such as a reaction accordingto the teachings herein.

Another aspect of the disclosure is directed at a polymeric compositionincluding one or more 1,1-disubstituted alkene monomers and one or moreadditives.

Another aspect of the disclosure is directed at a system forpolymerizing one or more monomers including a reactor having anagitation device for forming an emulsion; about 30 weight percent ormore water; about 10 weight percent or more of one or more monomersincluding one or more 1,1-disubstituted alkenes; and one or moresurfactants. Preferably the agitation device includes a stirring deviceor a sonication device. The system preferably includes an activator(s)for initiating anionic polymerization of 1,1-disubstituted alkenes.

Another aspect of the disclosure is directed at a block copolymer havinga first polymer block including a first primary monomer that is a1,1-disubstituted alkene compound, wherein the first primary monomer ispresent at a concentration of about 50 weight percent or more, based onthe total weight of the first polymer block, the first polymer blockcovalently bonded to a second polymer block including a second primarymonomer different from the first primary monomer, wherein the secondprimary monomer is present at a concentration of about 50 weight percentor more, based on the total weight of the second polymer block.

Another aspect of the disclosure is directed at a low molecular weightpolymer having a number average degree of polymerization from about 4 toabout 50, and the low molecular weight polymer includes about 60 weightpercent or more of one or more 1,1-disubstituted alkene compounds, basedon the total weight of the low molecular weight polymer. Preferably thelow molecular weight polymer includes a primary monomer present at about90 weight percent or more, based on the total weight of the lowmolecular weight polymer, and the primary monomer is one of the one ormore 1,1-disubstituted alkene compounds.

The methods according to the teachings herein may be employed to producea polymer including one or more 1,1-disubstituted alkene monomers havingimproved control of molecular weight, improved control of molecularweight distribution, or both. For example, the emulsion polymerizationmethods may be employed for controllably producing low molecular weightpolymers including a 1,1-disubstituted alkene monomer. The methodsaccording to the teachings herein may be employed to controllablyproduce high molecular weight polymers including a 1,1-disubstitutedalkene. The methods according to the teachings herein may be employed toproduce a random copolymer including two or more 1,1-disubstitutedalkene monomers having improved control of the monomer sequencedistribution. The methods according to the teachings herein may beemployed to produce a block copolymer including two different polymerblocks, the block copolymer including one or more 1,1-disubstitutedalkene monomers. The methods according to the teachings herein may beemployed to produce an emulsion having generally high polymerconcentration (e.g., about 10 weight percent or more) and/or having lowviscosity. The methods according to the teachings herein may be employedto produce polymers using anionic polymerization with a throughput rateof about 10 kg/hour or more and/or in a reactor system having a volume(e.g., of the emulsion) of about 20 liter or more. For example, themethods according to the teachings herein may better control thetemperature during the polymerization, even when using pilot scale ormanufacturing scale production (e.g., so that the process is generallyfree of temperature spikes during polymerization).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a drawing illustrating features of an emulsion system forpolymerizating of a polymer including a 1,1-disubstituted alkene monomeraccording to the teachings herein using anionic polymerization.

FIG. 2 is a diagram illustrating features of a process forpolymerizating a polymer including a 1,1-disubstituted alkene monomerusing anionic polymerization.

FIGS. 3A and 3B depict representative NMR spectrograms illustrating theconversion of monomer to polymer via emulsion polymerization. FIG. 3A istaken at an early stage of the polymerization reaction and the peak at6.45 ppm identifies the presence of unreacted monomer. FIG. 3B is takenat a later stage of the polymerization reaction and there is nodetectable peak at 6.45 ppm.

FIG. 4 is a representative GPC chromatogram employed for thecharacterization of the molecular weight distribution of a polymeraccording to the teachings herein.

DETAILED DESCRIPTION

Surprisingly, it has been found that a monomer including a1,1-disubstituted alkene capable of Michael addition with water ormoisture in the presence of an acid may be anionically polymerized usingan emulsion polymerization process. Furthermore, it has beensurprisingly been found that a polymer including a 1,1-disubstitutedalkene may be polymerized (e.g., using an anionic polymerizationprocess, such as an anionic emulsion polymerization process according tothe teachings herein) to controllably produce polymers (e.g., to producepolymers having controlled molecular weight and/or structure). In theemulsion polymerization process, two or more incompatible phases areformed including a continuous carrier fluid phase and discrete phaseincluding the monomer(s) and/or reaction products from thepolymerization of the monomer(s). The emulsion preferably includes asurfactant (i.e., an emulsifying agent) capable of improving thestability of the discrete phases. The methods according to the teachingsherein may be used to prepare a homopolymer or a copolymer. For example,the polymer may be a random copolymer or a block copolymer.

FIG. 1 illustrates features that may be employed in an emulsion systemaccording to the teachings herein. The emulsion system 10 includes acontinuous liquid phase 12 and a dispersed phase 14. The dispersed phasemay be in the form of micelles. The dispersed phase 14 includes asurfactant 16, which may be present as a surfactant layer 16. Thedispersed phase 14 has an interior that includes a monomer and/or apolymer 26. It will be appreciated that prior to a polymerizationreaction, the dispersed phase may include monomer 26 and besubstantially free of any polymer 26. After a polymerization reactionbegins, the dispersed phase may include both monomer and polymer 26. Themonomer may be completely converted so that eventually the dispersedphase includes polymer 26 and is substantially or entirely free ofmonomer. The surfactant layer 16 may have an inner surface 22 and anouter surface 20. The inner surface 22 may contact the monomer and/orthe polymer 26. The outer surface 20 may contact the continuous liquidphase 12. The continuous liquid phase 12 may include or consistsubstantially (e.g., about 90 volume percent or more or about 98 volumepercent or more based on the total volume of the continuous liquidphase) of a carrier liquid 28. The carrier liquid 28 preferably includeswater, and more preferably deionized water. The monomer 26 and/orpolymer 26 preferably includes one or more 1,1-disubstituted alkenecompounds.

The monomer includes one or more monomers capable of Michael additionwith water or moisture in the presence of an acid. The monomer typicallyincludes one or more 1,1-disubstituted alkene compounds (e.g., one ormore 1,1-disubstituted ethylene compounds. The 1,1-disubstituted alkenepreferably is a primary monomer (i.e., a monomer present at 50 weightpercent or more of a polymer block or of an entire polymer).1,1-disubstituted alkene compounds are compounds (e.g., monomers)wherein a central carbon atom is doubly bonded to another carbon atom toform an ethylene group. The central carbon atom is further bonded to twocarbonyl groups. Each carbonyl group is bonded to a hydrocarbyl groupthrough a direct bond or an oxygen atom. Where the hydrocarbyl group isbonded to the carbonyl group through a direct bond, a keto group isformed. Where the hydrocarbyl group is bonded to the carbonyl groupthrough an oxygen atom, an ester group is formed. The 1,1-disubstitutedalkene preferably has a structure as shown below in Formula I, where X¹and X² are an oxygen atom or a direct bond, and where R¹ and R² are eachhydrocarbyl groups that may be the same or different. Both X¹ and X² maybe oxygen atoms, such as illustrated in Formula IIA, one of X¹ and X²may be an oxygen atom and the other may be a direct bond, such as shownin Formula IIB, or both X¹ and X² may be direct bonds, such asillustrated in Formula IIC. The 1,1-disubstituted alkene compounds usedherein may have all ester groups (such as illustrated in Formula IIA),all keto groups (such as illustrated in Formula IIB) or a mixturethereof (such as illustrated in Formula IIC). Compounds with all estergroups are preferred due to the flexibility of synthesizing a variety ofsuch compounds.

One or more as used herein means that at least one, or more than one, ofthe recited components may be used as disclosed. Nominal as used withrespect to functionality means the theoretical functionality, generallythis can be calculated from the stoichiometry of the ingredients used.Generally, the actual functionality is different due to imperfections inraw materials, incomplete conversion of the reactants and formation ofby-products. Durability in this context means that the composition oncecured remains sufficiently strong to perform its designed function, inthe embodiment wherein the cured composition is an adhesive, theadhesive holds substrates together for the life or most of the life ofthe structure containing the cured composition. As an indicator of thisdurability, the curable composition (e.g., adhesive) preferably exhibitsexcellent results during accelerated aging. Residual content of acomponent refers to the amount of the component present in free form orreacted with another material, such as a polymer. Typically, theresidual content of a component can be calculated from the ingredientsutilized to prepare the component or composition. Alternatively, it canbe determined utilizing known analytical techniques. Heteroatom meansnitrogen, oxygen, sulfur and phosphorus, more preferred heteroatomsinclude nitrogen and oxygen. Hydrocarbyl as used herein refers to agroup containing one or more carbon atom backbones and hydrogen atoms,which may optionally contain one or more heteroatoms. Where thehydrocarbyl group contains heteroatoms, the heteroatoms may form one ormore functional groups well known to one skilled in the art. Hydrocarbylgroups may contain cycloaliphatic, aliphatic, aromatic or anycombination of such segments. The aliphatic segments can be straight orbranched. The aliphatic and cycloaliphatic segments may include one ormore double and/or triple bonds. Included in hydrocarbyl groups arealkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, alkaryl andaralkyl groups. Cycloaliphatic groups may contain both cyclic portionsand noncyclic portions. Hydrocarbylene means a hydrocarbyl group or anyof the described subsets having more than one valence, such as alkylene,alkenylene, alkynylene, arylene, cycloalkylene, cycloalkenylene,alkarylene and aralkylene. One or both hydrocarbyl groups may consist ofone or more carbon atoms and one or more hydrogen atoms. As used hereinpercent by weight or parts by weight refer to, or are based on, theweight of the emulsion composition unless otherwise specified.

Unless defined otherwise, all technical and scientific terms used hereinhave the meaning commonly understood by a person skilled in the art towhich this disclosure belongs. The following references provide one ofskill with a general definition of many of the terms used in thisdisclosure: Singleton et al., Dictionary of Microbiology and MolecularBiology (2nd ed. 1994); The Cambridge Dictionary of Science andTechnology (Walker ed., 1988); The Glossary of Genetics, 5th Ed., R.Rieger et al. (eds.), Springer Verlag (1991); and Hale & Marham, TheHarper Collins Dictionary of Biology (1991). As used herein, thefollowing terms have the meanings ascribed to them below, unlessspecified otherwise.

1,1-disubstituted alkene compound means a compound having a carbon witha double bond attached thereto and which is further bonded to two carbonatoms of carbonyl groups. A preferred class of 1,1-disubstituted alkenecompounds are the methylene malonates which refer to compounds havingthe core formula

The term “monofunctional” refers to 1,1-disubstituted alkene compoundsor a methylene malonates having only one core formula. The term“difunctional” refers to 1,1-disubstituted alkene compounds or amethylene malonates having two core formulas bound through a hydrocarbyllinkage between one oxygen atom on each of two core formulas. The term“multifunctional” refers to 1,1-disubstituted alkene compounds ormethylene malonates having more than one core formula which forms achain through a hydrocarbyl linkage between one oxygen atom on each oftwo adjacent core formulas. The term “latent acid-forming impurities” or“latent acid-forming impurity” refers to any impurity that, if presentalong with the 1,1-disubstituted alkene compounds or methylenemalonates, will with time be converted to an acid. The acid formed fromthese impurities may result in overstabilization of the1,1-disubstituted alkene compounds, thereby reducing the overall qualityand reactivity of the compounds. The term “ketal” refers to a moleculehaving a ketal functionality; i.e., a molecule containing a carbonbonded to two —OR groups, where O is oxygen and R represents any alkylgroup. The terms “volatile” and “non-volatile” refers to a compoundwhich is capable of evaporating readily at normal temperatures andpressures, in the case of volatile; or which is not capable ofevaporating readily at normal temperatures and pressures, in the case ofnon-volatile. As used herein, the term “stabilized” (e.g., in thecontext of “stabilized” 1,1-disubstituted alkene compounds or monomercompositions comprising same) refers to the tendency of the compounds(or the monomer compositions), prior to activation with an activator, tosubstantially not polymerize with time, to substantially not harden,form a gel, thicken, or otherwise increase in viscosity with time,and/or to substantially show minimal loss in cure speed (i.e., curespeed is maintained) with time. As used herein, the term “shelf-life”(e.g., as in the context of 1,1-disubstituted alkene compounds having animproved “shelf-life”) refers to the 1,1-disubstituted alkene compoundswhich are stabilized for a given period of time; e.g., 1 month, 6months, or even 1 year or more.

The hydrocarbyl groups (e.g., R¹ and R²), each comprise straight orbranched chain alkyl, straight or branched chain alkyl alkenyl, straightor branched chain alkynyl, cycloalkyl, alkyl substituted cycloalkyl,aryl, aralkyl, or alkaryl. The hydrocarbyl group may optionally includeone or more heteroatoms in the backbone of the hydrocarbyl group. Thehydrocarbyl group may be substituted with a substituent that does notnegatively impact the ultimate function of the monomer or the polymerprepared from the monomer. Preferred substituents include alkyl, halo,alkoxy, alkylthio, hydroxyl, nitro, cyano, azido, carboxy, acyloxy, andsulfonyl groups. More preferred substituents include alkyl, halo,alkoxy, alylthio, and hydroxyl groups. Most preferred substituentsinclude halo, alkyl, and alkoxy groups.

As used herein, alkaryl means an alkyl group with an aryl group bondedthereto. As used herein, aralkyl means an aryl group with an alkyl groupbonded thereto and include alkylene bridged aryl groups such as diphenylmethyl groups or diphenyl propyl groups. As used herein, an aryl groupmay include one or more aromatic rings. Cycloalkyl groups include groupscontaining one or more rings, optionally including bridged rings. Asused herein, alkyl substituted cycloalkyl means a cycloalkyl grouphaving one or more alkyl groups bonded to the cycloalkyl ring.

Preferred hydrocarbyl groups include 1 to 30 carbon atoms, morepreferably 1 to 20 carbon atoms, and most preferably 1 to 12 carbonatoms. Preferred hydrocarbyl groups with heteroatoms in the backbone arealkyl ethers having one or more alkyl ether groups or one or morealkylene oxy groups. Preferred alkyl ether groups are ethoxy, propoxy,and butoxy. Preferably such compounds contain from about 1 to about 100alkylene oxy groups and more preferably about 1 to about 40 alkylene oxygroups and more preferably from about 1 to about 12 alkylene oxy groups,and most preferably from about 1 to about 6 alkylene oxy groups.

One or more of the hydrocarbyl groups (e.g., R¹, R², or both),preferably includes a C₁₋₁₅ straight or branched chain alkyl, a C₁₋₁₅straight or branched chain alkenyl, a C₅₋₁₈ cycloalkyl, a C₆₋₂₄ alkylsubstituted cycloalkyl, a C₄₋₁₈ aryl, a C₄₋₂₀ aralkyl, or a C₄₋₂₀aralkyl. More preferably, the hydrocarbyl group, includes a C₁₋₈straight or branched chain alkyl, a C₅₋₁₂ cycloalkyl, a C₆₋₁₂ alkylsubstituted cycloalkyl, a C₄₋₁₈ aryl, a C₄₋₂₀ aralkyl, or a C₄₋₂₀aralkyl.

Preferred alkyl groups include methyl, propyl, isopropyl, butyl,tertiary butyl, hexyl, ethyl pentyl, and hexyl groups. More preferredalkyl groups include methyl and ethyl. Preferred cycloalkyl groupsinclude cyclohexyl and fenchyl. Preferred alkyl substituted groupsinclude menthyl and isobornyl.

Most preferred hydrocarbyl groups attached to the carbonyl group includemethyl, ethyl, propyl, isopropyl, butyl, tertiary, pentyl, hexyl, octyl,fenchyl, menthyl, and isobornyl.

Particularly preferred monomers include methyl propyl methylenemalonate, dihexyl methylene malonate, di-isopropyl methylene malonate,butyl methyl methylene malonate, ethoxyethyl ethyl methylene malonate,methoxyethyl methyl methylene malonate, hexyl methyl methylene malonate,dipentyl methylene malonate, ethyl pentyl methylene malonate, methylpentyl methylene malonate, ethyl ethylmethoxy methylene malonate,ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate,dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxyethyl methylene malonate, dimethyl methylene malonate, di-N-propylmethylene malonate, ethyl hexyl methylene malonate, methyl fenchylmethylene malonate, ethyl fenchyl methylene malonate, 2 phenylpropylethyl methylene malonate, 3 phenylpropyl ethyl methylene malonate, anddimethoxy ethyl methylene malonate.

Some or all of the 1,1-disubstituted alkenes can also be multifunctionalhaving more than one core unit and thus more than one alkene group.Exemplary multifunctional 1,1-disubstituted alkenes are illustrated bythe formula:

wherein R¹, R² and X are as previously defined; n is an integer of 1 orgreater; and R is a hydrocarbyl group, and the 1,1-disubstituted alkenehas n+1 alkenes. Preferably n is 1 to about 7, and more preferably 1 toabout 3, and even more preferably 1. In exemplary embodiments R² is,separately in each occurrence, straight or branched chain alkyl,straight or branched chain alkenyl, straight or branched chain alkynyl,cycloalkyl, alkyl substituted cycloalkyl, aryl, aralkyl, or alkaryl,wherein the hydrocarbyl groups may contain one or more heteroatoms inthe backbone of the hydrocarbyl group and may be substituted with asubstituent that does not negatively impact the ultimate function of thecompounds or polymers prepared from the compounds. Exemplarysubstituents are those disclosed as useful with respect to R¹. Incertain embodiments R² is, separately in each occurrence, C₁₋₁₅ straightor branched chain alkyl, C₂₋₁₅ straight or branched chain alkenyl, C₅₋₁₈cycloalkyl, C₆₋₂₄ alkyl substituted cycloalkyl, C₄₋₁₈ aryl, C₄₋₂₀aralkyl or C₄₋₂₀ aralkyl groups. In certain embodiments R² is separatelyin each occurrence C₁₋₈ straight or branched chain alkyl, C₅₋₁₂cycloalkyl, C₆₋₁₂ alkyl substituted cycloalkyl, C₄₋₁₈ aryl, C₄₋₂₀aralkyl or C₄₋₂₀ alkaryl groups.

It will be appreciated according to the teaching herein, the one or moremonomer may include a comonomer that is a 1,1-disubstituted alkenecompound having a hydrocarbyl group bonded to each of the carbonylgroups through a direct bond (e.g., a carbon-carbon bond) or an oxygenatom, such as a monomer having one or more features described above. Ifincluded, a comonomer may optionally be a monomer that is not a1,1-disubstituted alkene compound. Any comonomer capable of anionicpolymerization may be employed. For example, the comonomer may becapable of forming a random copolymer with a 1,1-disubstituted alkenecompound, capable of forming a block copolymer with a 1,1-disubstitutedalkene compound, or both.

The 1,1-disubstituted alkene compound preferably is prepared using amethod which results in a sufficiently high purity so that it can bepolymerized. The purity of the 1,1-disubstituted alkene compound may besufficiently high so that 70 mole percent or more, preferably 80 molepercent or more, more preferably 90 mole percent or more, even morepreferably 95 mole percent or more, and most preferably 99 mole percentor more of the 1,1-disubstituted alkene compound is converted to polymerduring a polymerization process. The purity of the 1,1-disubstitutedalkene compound preferably is about 85 mole percent or more, morepreferably about 90 mole percent or more, even more preferably about 93mole percent or more, even more preferably about 95 mole percent ormore, even more preferably about 97 mole percent or more, and mostpreferably about 97 mole percent or more, based on the total weight ofthe 1,1-disubstituted alkene compound. If the 1,1-disubstitute alkenecompound includes impurities, preferably about 40 mole percent or more,more preferably about 50 mole percent or more of the impurity moleculesare the analogous 1,1-disubstituted alkane compound. The concentrationof any impurities having a dioxane group preferably is about 2 molepercent or less, more preferably about 1 mole percent or less, even morepreferably about 0.2 mole percent or less, and most preferably about0.05 mole percent or less, based on the total weight of the1,1-disubstituted alkene compound. The total concentration of anyimpurity having the alkene group replaced by an analogous hydroxyalkylgroup (e.g., by a Michael addition of the alkene with water), preferablyis about 3 mole percent or less, more preferably about 1 mole percent orless, even more preferably about 0.1 mole percent or less, and mostpreferably about 0.01 mole percent or less, based on the total moles inthe 1,1-disubstituted alkene compound. Preferred 1,1-disubstitutedalkene compounds are prepared by a process including one or more (e.g.,two or more) steps of distilling a reaction product or an intermediatereaction product (e.g., a reaction product or intermediate reactionproduct of a source of formaldehyde and a malonic acid ester).

The polymerization process preferably includes one or more surfactantsfor forming an emulsion having micelles or a discrete phase including amonomer (e.g., a 1,1-disubstituted alkene compound) distributedthroughout a continuous phase (e.g., a continuous phase including acarrier liquid). The surfactant may be an emulsifier, a defoamer, or awetting agent. The surfactant preferably is present in a sufficientquantity so that a stable emulsion is formed by mixing or otherwiseagitating a system including the monomer and carrier liquid. Thesurfactants according to the teachings herein include one or moresurfactants for improving the stability of emulsion (i.e., for improvingthe stability of the dispersed phase in the carrier liquid phase). Thesurfactant and/or the amount of surfactant is preferably selected sothat all of the monomer micelles are covered by a layer of thesurfactant.

The surfactant may include a first end that is hydrophobic and anopposing second end that is hydrophilic. The surfactant may include onesegment (e.g., one end) of the surfactant having a dipole moment (inabsolute value) greater than about 0.1 debye.

The surfactant may include an amphoteric surfactant, a nonionicsurfactant, or any combination thereof. The surfactant preferably isfree of anionic surfactants during the polymerization process.

Surfactants that may be employed include alkyl polysaccharides,alkylamine ethoxylates, amine oxides, castor oil ethoxylates,ceto-oleyl, ceto-stearyl, decyl alcohol ethoxylates, dinonyl phenolethoxylates, dodecyl phenol ethoxylates, end-capped ethoxylates,ethoxylated alkanolamides, ethylene glycol esters, fatty acidalkanolamides, fatty alcohol alkoxylates, lauryl, mono-branched, nonylphenol ethoxylates, octyl phenol ethoxylates, random copolymeralkoxylates, sorbitan ester ethoxylates, stearic acid ethoxylates,synthetic, tall oil fatty acid ethoxylates, tallow amine ethoxylates,alkyl ether phosphates, alkyl phenol ether phosphates, alkyl phenolether sulfates, alkyl naphthalene sulfonates, condensed naphthalenesulfonates, aromatic hydrocarbon sulphonic acids, fatty alcoholsulfates, alkyl ether carboxylic acids and salts, alkyl ether sulfates,mono-alkyl sulphosuccinamates, di-alkyl sulphosuccinates, alkylphosphates, alkyl benzene sulphonic acids and salts, alpha olefinsulfonates, condensed naphthalene sulfonates, polycarboxylates, alkyldimethylamines, alkyl amidopropylamines, quaternised amine ethoxylates,quaternary ammonium compounds, and mixtures or combinations thereof.

Non-limiting examples of amphoteric surfactants that may be employedinclude amine oxide surfactants, sultaine surfactants, betainesurfactants, or any combination thereof. Preferred sultaine and betainesurfactants include hydroxysultaines and hydroxybutaines. Withoutlimitation, exemplary amphoteric surfactants that may be employedinclude cocamine oxide, cocoamidopropylamine oxide, cetamine oxide,decylamine oxide, lauramine oxide, myristylamine oxide, cetyl amineoxide, steramine oxide, cocamidopropyl hydroxysultaine,capryl/capramidopropyl betaine, cocamidopropyl betaine, cetyl betaine,cocamidopropyl betaine, laurylamidopropyl betaine, or any combinationthereof.

Non-limiting examples of cationic surfactants include quaternaryammonium chloride surfactants, quaternary ammonium methyl sulfatesurfactants, ester quaternarie surfactants, or any combination thereof.Without limitation, exemplary cationic surfactants that may be employedinclude cetrimonium chloride, stearalkonium chloride, olealkoniumchloride, stearamidopropalkonium chloride, alkyl dimethyl benzylammonium chlorides, alkyl dimethyl ethylbenzyl ammonium chlorides,didecyl dimethyl ammonium chloride, dialkyl dimethyl ammonium chloride,benzalkonium chloride, methyl bis(hydrogenated tallowamidoethyl)-2-hydroxyethyl amonium methyl sulfate, methylbis(tallowamido ethyl)-2-hydroxyethyl ammonium methyl sulfate, methylbis(tallowamido ethyl)-2-tallow imidazolinium methyl sulfate, dialkylammonium methosulfate, dialkylester ammonium methosulfate,dipalmitoylethyl hydroxyethylmmonium methosulfate, dialkyl ammoniummethosulfate, dialkylester ammonium methosulfate, methyl bis[ethyl(tallowate)]-2-hydroxyethyl ammonium methyl sulfate, methyl bis[ethyl(tallowate)]-2-hydroxyethyl ammonium methyl sulfate, or any combinationthereof.

Non-limiting examples of nonionic surfactants include alkoxylatesurfactants, amide surfactants, ester surfactants, ethoxylatesurfactants, lactate surfactants, triglyceride surfactants, or anycombination thereof. Without limitation, exemplary nonionic surfactantsthat may be employed include polyalkoxylated alphatic bases,polyalkoxylated amides, alkylphenol alkoxylates, alkylphenol blockcopolymers, alkyl phenol ethoxylates, polyalkylene oxide blockcopolymers, glyceryl cocoate, alcohol alkoxylates, butyl based blockcopolymers, polyalkylene oxide block copolymer, N, N-dimethyldecanamide(N, N-dimethylcapramide), N, N-dimethyloctanamide (N,N-dimethylcaprylamide), fatty alkanolamides, oleyl diethanolamide,lauryl diethanolamide, coco diethanolamide, fatty diethanolamides,polyethylene glycol cocamides, polyethylene glycol lauramides, laurylmonoethanolamide, myristyl monoethanolamide, coco monoisopropanolamide,alkyl ether phosphates, phosphate esters, glyceryl monostearate,glycerol monooleate, polyglyceryl decaoleates, polyglycerol esters,polyglycerol polyricinoleates, neutralized alcohol phosphates, caprictriglyceride, caprylic triglyceride, tridecyl alcohol phosphate ester,nonylphenol ethoxylate phosphate ester, trimethylopropane tricaprylatetricaprate polyol ester, methyl caprylate/caprate, methyl laurate,methyl myristate, methyl palmitate, methyl oleate, alcohol phosphates,trimethylolpropane tricaprylate/caprate polyol ester, pentaerythritoltricaprylate/caprate polyol ester, pentaerythrityltetracaprylate/tetracaprate, nonylphenol phosphate ester, phosphateesters of an alkyl polyethoxyethanol, canola oil methyl ester, soybeanoil methyl ester, pentaerythritol tetracaprylate/caprate,trimethylolpropane tricaprylate/caprate, amine neutralized phosphateester, fatty alkyl ethoxylates, alcohol ethoxylates, fatty acidethoxylates, tallow amine ethoxylates, octyl phenol ethoxylates, nonylphenol ethoxylate, castor oil ethoxylate, polyalkoxylated alphaticbases, polyalkoxylated amides, octyl phenol ethoxylate, tristyrylphenolethoxylate, ammonium salt of ethoxylated polyarylphenol sulfates,tristyrylphenol ethoxylate phosphate ester, potassium salt oftristyrylphenol ethoxylate phosphate ester, ethoxylated coco amine,sorbital trioleate ethoxylate, sorbital monooleate ethoxylate, lauryllactyl lactate, capric triglyceride, caprylic triglyceride, hydrogenatedvegetable oil, or any combination thereof.

One example of a preferred surfactant (e.g., an emulsifier) is anethoxylate, such as an ethoxylated diol. For example, the surfactant mayinclude 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylate. The surfactantmay include a poly(alkene glycol). Another example of a preferredsurfactant is a poly(ethylene glycol)-block-poly(propyleneglycol)-block-poly(ethylene glycol) copolymer. Another example of apreferred surfactant is a surfactant including an alcohol, anethoxylated alcohol, or both. For example, the surfactant may includeCARBOWET® 138 nonionic surfactant (including alkyl alcohol, polyethyleneglycol, ethoxylated C9-C11 alcohols). Another example of a preferredsurfactant is a surfactant including a sorbitan, a sorbitol, or apolyoxyalkene. For example, the surfactant may include sorbitanmonopalmitate (nonionic surfactant). Other examples of preferredsurfactants include branched polyoxyethylene (12) nonylphynyl ether(IGEPAL® CO-720) and poly(ethylene glycol) sorbitol hexaoleate (PEGSH).

The amount of the surfactant (e.g., the amount of the emulsifier)preferably is sufficient to form a layer that substantially encapsulatesthe monomer and subsequent polymer particles. The amount of surfactantpreferably is sufficient so that the discrete phase has a diameter ofabout 10 mm or less, about 1 mm or less, about 300 μm or less, or about100 μm or less. The amount of the surfactant is preferably sufficient sothat the discrete phase has a diameter of about 0.01 μm or more, about0.1 μm or more, about 1 μm or more, about 10 μm or more, or about 50 μmor more. The concentration of the surfactant may be about 0.001 weightpercent or more, preferably about 0.01 weight percent or more, morepreferably about 0.1 weight percent or more, and most preferably about0.5 weight percent or more, based on the total weight of the emulsion.The concentration of the surfactant may be about 15 weight percent orless, preferably about 10 weight percent or less, and more preferablyabout 6 weight percent or less, and most preferably about 3 weightpercent or less, based on the total weight of the emulsion. The weightratio of the surfactant to the total weight of the monomer and polymerin the emulsion (e.g., at the end of the polymerization process)preferably is about 0.0001 or more, more preferably about 0.002 or more,even more preferably about 0.005 or more, and most preferably about 0.01or more. The weight ratio of the surfactant to the total weight of themonomer and polymer in the emulsion (e.g., at the end of thepolymerization process) preferably is about 5 or less (i.e., about 5:1or less), more preferably about 1 or less, even more preferably about0.5 or less, and most preferably about 0.1 or less.

The surfactant is preferably added prior to the polymerization process.However, it will be appreciated that one or more surfactants may beadded following a polymerization process (e.g., following an emulsionpolymerization process). For example, a surfactant may be addedfollowing a polymerization process to stabilize an emulsion (such as forlong term stability of about 1 week or more, about 1 month or more, orabout 3 months or more).

The carrier liquid may be any liquid which is not a solvent for the oneor more monomers. The carrier liquid may include water, a glycol, analcohol, a ketone, an alkane, an aprotic compound, an ester, an ether,acetone, an acetate, a hydrofuran, a phenyl or a compound including oneor more aryl groups, or any combination thereof. More preferred carrierliquids include water, a glycol, an alcohol, a ketone, or anycombination thereof. Even more preferred carrier liquids include water,ethylene glycol, methanol, a monoalkyl ether of ethylene glycol, or anycombination thereof. Preferred carrier liquids include a single compoundor include a mixture of compounds that are miscible, e.g., so that thecarrier liquid is a single phase. The carrier liquid may have a freezingpoint of about 10° C. or less, and preferably about 0° C. or less.

Preferably the carrier liquid includes, consists essentially of, orconsists entirely of water. For example, the carrier liquid may consistentirely of deionized water. The quality of the water may play animportant role. For example, the presence of foreign ions can interferewith the initiation process, efficacy of the surfactant(s), andsubsequent pH control. Preferably, the concentration of foreign ions(i.e., ions other than H3O+ and OH−) in the water is sufficiently low sothat the water meets the requirements of class 3 or better, class 2 orbetter, or class 1 or better, as measured according to ISO 3696. Theconductivity of the water preferably is about 10 mS/m or less, morepreferably about 1 mS/m or less, even more preferably about 100 μS/m orless, and most preferably about 10 μS/m or less. The conductivity of thewater may be about 0 or more, about 0.1 μS/m or more, or about 1 μS/m ormore.

The emulsion polymerization may be initiated using an activator capableof initiating anionic polymerization of the 1,1-disubstituted alkenecontaining compound. The activator may be a compound that is anucleophile or a compound that forms a nucleophile. Examples ofactivators (i.e., initiators), which may be employed, include ionicmetal amides, hydroxides, cyanides, phosphines, alkoxides, amines andorganometallic compounds (such as alkyllithium compounds), and metalbenzoates. The polymerization activator may have one or more of thefeatures (e.g., include one or any combinations of the activating agentsand/or polymerization activators, include an activating agent at aconcentration or concentration range, or include a process step) asdescribed in US patent Application publication US 2015/0073110 A1,published on Mar. 12, 2015, incorporated herein by reference (e.g., seeparagraphs 0024 to 0050). By way of example, the activator may include,consist essentially of, or consist entirely of one or more metalbenzoates, such as sodium benzoate. As an alternative to using anactivator, the polymerization may be activated using a source ofradiation, preferably UV light. The molecular weight of the polymer maybe adjusted by adjusting the molar ratio of the monomer to theactivator. Preferably the molar ratio of the monomer to activator isabout 25 or more, about 50 or more, about 100 or more, about 500 ormore, or about 1,000 or more. The molar ratio of the monomer to theactivator preferably is about 100,000 or less, about 50,000 or less,about 10,000 or less, or about 2,000 or less.

According to certain embodiments, a suitable polymerization activatorcan generally be selected from any agent that can initiatepolymerization substantially upon contact with a selected polymerizablecomposition. In certain embodiments, it can be advantageous to selectpolymerization initiators that can induce polymerization under ambientconditions and without requiring external energy from heat or radiation.In embodiments wherein the polymerizable composition comprises one ormore 1,1-disubstituted alkene compounds, a wide variety ofpolymerization initiators can be suitable including most nucleophilicinitiators capable of initiating anionic polymerization. For example,suitable initiators include alkali metal salts, alkaline earth metalsalts, ammonium salts, amine salts, halides (halogen containing salts),metal oxides, and mixtures containing such salts or oxides. Exemplaryanions for such salts include anions based on halogens, acetates,benzoates, sulfur, carbonates, silicates and the like. The mixturescontaining such salts can be naturally occurring or synthetic. Specificexamples of suitable polymerization initiators for 1,1-disubstitutedalkene compounds can include ionic compounds such as sodium silicate,sodium benzoate, and calcium carbonate. Additional suitablepolymerization initiators for such polymerizable compositions are alsodisclosed in U.S. Patent Application Publication No. 2015/0073110, whichis hereby incorporated by reference.

The emulsion and/or one or more of the monomers (e.g., the1,1-disubstituted alkene compounds) may further contain other componentsto stabilize the monomer prior to exposure to polymerization conditionsor to adjust the properties of the final polymer for the desired use.

Prior to the polymerization reaction, one or more inhibitors may beadded to reduce or prevent reaction of the monomer.

An acid containing compound may be employed in the emulsionpolymerization process. With various monomers, the use of an acidcontaining compound may be employed to reduce the reaction rate,decrease the polydispersity, or both. An additional benefit is theformation of stable monomer droplets and polymer particles (i.e.,decreasing likely coalescence and/or aggregation). When theconcentration of the acid containing compound is too high, thepolymerization reaction may be too slow for commercial viability. Whenthe concentration of the acid containing compound is too low, thepolymerization reaction may result in a polymer having highpolydispersity index. The acid containing compound may be a compound(e.g., an emulsifier or other surfactant) capable of forming an emulsionof the monomer in the carrier liquid without the use of othersurfactants. However, if the acid containing compound is capable offunctioning as a surfactant, it is preferred that a second surfactant(such as a surfactant that does not form an acid) be employed. The acidcontaining compound may be an organic compound having one or more acidgroups. For example, the acid containing compound may include one ormore acid groups having a sulfur, phosphorous, chlorine, or bromine,fluorine or nitrogen atom. The acid containing compound preferablyincludes one or more nitrogen atoms (such as in a nitrate or nitritegroup) and/or one or more sulfur atoms (such as in a sulfonate group). Aparticularly preferred acid containing compound is4-dodecylbenzenesulfonic acid (DBSA). It is known that DBSA, in anincompatible or biphasic mixture, will orient in such a way as toprovide protons at the monomer-water interface (e.g., primarily on thewater side of the interface) thereby inducing functional inhibition ortermination of the reactive monomer and/or propagating polymer chain. Itwill be appreciated that other acid containing surfactants may similarlyaffect the initiation, propagation, or termination of the polymer.Preferably, the weight ratio of the acid containing compound to thetotal weight of the surfactant is about 0.6 or less, more preferablyabout 0.3 or less, even more preferably 0.1 or less, and most preferablyabout 0.05 or less. Preferably, the weight ratio of the acid containingcompound to the total weight of the surfactant is about 0.001 or more,more preferably about 0.005 or more, and most preferably about 0.01 ormore. The weight ratio of the acid containing compound to the amount ofthe monomer employed for a polymerization step (e.g., for polymerizing afirst polymer block) preferably is about 0.00005 or more, morepreferably about 0.0002 or more and most preferably about 0.0005 ormore. The weight ratio of the acid containing compound to the amount ofthe monomer employed for a polymerization step (e.g., for polymerizing afirst polymer block) preferably is about 0.2 or less, more preferablyabout 0.04 or less, and most preferably about 0.005 or less.

The polymerization process may include a step of applying shear forcesor sonication to a mixture including at least the surfactant and thecarrier fluid for forming an emulsion. For example, the process mayinclude stirring or otherwise agitating the mixture for creating theemulsion.

The polymerization process may be a batch process (e.g., using a singlebatch reactor or a series of batch reactors). The polymerization processmay be in a continuous process, such as a process that transports anemulsion along the length of a reactor. In a batch process, or in acontinuous process, all of the monomer may be added at a single stage(e.g., prior to the addition of the polymerization activator, or at ornear the start of the polymerization reaction) or may be added atmultiple stages in the polymerization reaction.

The polymerization process may be employed for polymerization of ahomopolymer or a copolymer, such as a random copolymer or a blockcopolymer. The homopolymer or copolymer includes one or more1,1-disubstituted alkene containing compounds according to the teachingsherein. Preferably, the amount of the 1,1-disubstituted alkenecontaining compounds in the polymer is about 5 weight percent or more,more preferably about 30 weight percent or more, even more preferablyabout 50 weight percent or more, even more preferably about 70 weightpercent or more, based on the total weight of the emulsion polymer. Forexample, one or more of the polymer blocks may consist essentially of,or entirely of the 1,1-disubstituted alkene containing compounds.

A multi-stage addition of monomer may be employed for polymerization ofa block copolymer having polymer blocks with different compositions. Forexample, a block copolymer may have a first polymer block, (block A),and a second polymer block (block B). The block copolymer may have 2 ormore blocks or 3 or more blocks. The A block and B block may include atleast one monomer that is the same (however at differentconcentrations), or may include only monomers that are different. Forexample, the A block may be a homopolymer of a first monomer, and the Bblock may include one or more second monomers which are each differentfrom the first monomer. The first polymer block may be a homopolymer ora copolymer (e.g., a random copolymer). The second polymer block may bea homopolymer or a copolymer (e.g., a random copolymer). The firstpolymer block and the second polymer block preferably each include oneor more 1,1-disubstituted alkene containing compounds according to theteachings herein. Preferably, the amount of the 1,1-disubstituted alkenecontaining compounds in the first polymer block and/or in the secondpolymer block may be about 30 weight percent or more, preferably about50 weight percent or more, even more preferably about 70 weight percentor more, based on the total weight of the polymer block. For example,one or more of the polymer blocks may consist essentially of, orentirely of the 1,1-disubstituted alkene containing compounds. It willbe appreciated that one or more blocks may be substantially or entirelyfree of any 1,1-disubstituted alkene containing compounds. For example,one or more of the polymer blocks may include one or more conjugateddiene monomers and/or one or more styrenic monomers.

During the polymerization process, the emulsion is preferably stirred orotherwise agitated to create and/or maintain the micelle structure. Forexample, the emulsion including the monomer, the emulsifying agent, andthe carrier liquid may be mixed at a rate of 10 rpm or more, 50 rpm ormore, 200 rpm or more, or 1,000 rpm or more.

The emulsion polymerization process preferably includes a reactiontemperature at which the partial pressure of the carrier liquid isgenerally low. For example, the partial pressure of the carrier liquidmay be about 400 Torr or less, about 200 Torr or less, about 100 Torr orless, about 55 Torr or less, or about 10 Torr or less. The reactiontemperature preferably is about 80° C. or less, more preferably about70° C. or less, even more preferably about 60° C. or less, even morepreferably about 55° C. or less, even more preferably about 45° C. orless, even more preferably about 40° C. or less, and most preferablyabout 30° C. or less. The reaction temperature typically is sufficientlyhigh that the carrier liquid is in a liquid state. For example, thereaction temperature may be about −30° C. or more, about −10° C. ormore, or about 10° C. or more, or about 15° C. or more.

When polymerizing a 1,1-disubstituted alkene compound, it may bedesirable to add one or more acid compounds to the emulsion, to themonomer, or both, so that the initial pH of the emulsion is about 7 orless, about 6.8 or less, about 6.6 or less, or about 6.4 or less. It isbelieved that such an initial acidic condition may be beneficial forcontrolling or otherwise limiting the initiation of the monomer. Forexample, the 1,1-disubstituted alkene compound may be a compound thatwill auto-initiate under basic conditions and the use of an acidcondition may prevent or minimize such auto-initiation. The acidiccondition preferably is maintained throughout the polymerizationprocess. If the pH is too low, the reaction rate may be low or thereaction may be terminated. Preferably, the pH during the reaction isabout 5 or more, more preferably about 5.5 or more, even more preferablyabout 5.9 or more, and most preferably about 6 or more. It will beappreciated that following the polymerization process the pH may beadjusted to increase or decrease the pH. Preferably following thepolymerization process, the pH is reduced so that the difference betweenthe initial pH (during the reaction) and a later pH is about 0.2 ormore, more preferably about 0.3 or more, even more preferably about 0.4or more and most preferably about 0.5 or more. For example, the processmay include a step of decreasing the pH to a range of about 4.0 to about6.2, to a range of about 4.5 to about 6.0, to a range of about 5.0 toabout 6.0, or to a range of about 5.3 to about 5.9. Following a step ofpolymerizing a 1,1-disubstituted alkene compound and/or following a stepof separating the polymer from any residual monomer, the process mayinclude a step of increasing the pH (e.g. to about 6.5 or more, to about6.9 or more, or to about 7 or more).

The concentration of the carrier liquid in the emulsion compositionpreferably is sufficiently high so that the micelles of the emulsion donot agglomerate. The concentration of the carrier liquid may besufficiently high so that the carrier liquid functions as a heat sinkand minimizes any spikes in temperature during polymerization to about30° C. or less, more preferably about 15° C. or less, even morepreferably about 10° C. or less, and most preferably about 5° C. orless. The concentration of the carrier liquid may be sufficiently highso that the emulsion is capable of flowing even after the polymerizationreaction is complete. For example, the ratio of the zero shear viscosity(measured at 25° C.) of the emulsion to the zeros shear viscosity of thepolymer produced by the emulsion polymerization process may be about 0.2or less, about 0.1 or less, about 0.02 or less, or about 0.005 or less,or about 0.001 or less. The viscosity ratio may be 0 or more.Preferably, the concentration of the carrier liquid is about 25 weightpercent or more, even more preferably about 30 weight percent or more,even more preferably about 35 weight percent or more, and mostpreferably about 40 weight percent or more. The concentration of thecarrier liquid should be sufficiently low so that the polymerizationprocess is economical. Preferably the concentration of the carrierliquid is about 98 weight percent or less, more preferably about 80weight percent or less, even more preferably about 70 weight percent orless, and most preferably about 65 weight percent or less.

The emulsion polymerization process may be stopped prior to thecompletion of the polymerization reaction or may be continued until thecompletion of the polymerization reaction. Preferably, the reaction rateis sufficiently high and/or the reaction time is sufficiently long sothat the polymerization reaction is substantially complete. For examplethe conversion of the monomer to polymer may be about 80 weight percentor more, about 90 weight percent or more, about 95 weight percent ormore, about 98 weight percent or more, about 99 weight percent or more.The conversion of monomer to polymer may be about 100 weight percent orless.

With reference to FIG. 2, the emulsion polymerization process 30typically includes a step of developing a multi-phase emulsion system32. For example, the process may include a step of combining a carrierliquid, a surfactant, and a monomer. It will be appreciated that thecomponents of the emulsion may be added at one time, may be added atdifferent times, or some components may be combined separately. Thedevelopment of the multi-phase emulsion system 32 typically requiresagitation. Depending on the type and intensity of the agitation (alongwith other factors such as the relative concentration of the monomer andthe surfactant), it may be possible to control the particle size of adispersed phase in the multi-phase emulsion system 32. The processtypically includes a step of initiating the polymerization reaction 34.The initiation step preferably occurs after micelles including themonomer have been established. As such, the process may include a stepof an activator migrating from the carrier liquid (continuous phase) andinto a micelle (e.g., by passing through the surfactant layer). It willbe appreciated that an activator may be added into the system prior tothe addition of monomer, at the same time as the addition of themonomer, or after addition of a first portion of the monomer and priorto the addition of a second portion of the monomer. After activation ofthe monomer, the process includes a step of propagating the polymer byan anionic polymerization reaction 36. The propagating step may continueuntil all of the monomer is consumed, or until the propagation reactionis stopped, such as by quenching 38 or the conditions are altered sothat further anionic polymerization reaction stops. The propagation stepmay also stop by a phase separation of the polymer from the monomer(e.g., where the monomer has difficulty in contacting the reactive endof the polymer molecule). Prior to a step of quenching, there may be oneor more additional steps of feed monomer (which may be the same ordifferent from the initial monomer feed), and one or more additionalsteps of propagating the polymerization reaction. With each suchpropagating step, the polymer molecular weight generally increases,unless conditions for addition chain activation are provided (forexample by adding additional activator). It will be appreciated that theresulting polymer may be capable of further reaction with monomer andmay thus be a “living” polymer.

The conversion of monomer to polymer may be measured using NMRspectroscopy, such as illustrated in FIG. 3A and FIG. 3B, correspondingto an early and a later stage of a propagation reaction for polymerizinga 1,1-disubstituted alkene monomer. Here, the monomer is diethylmethylene malonate and the concentration of the monomer can be monitoredby the peak at about 6.45 ppm 40 corresponding to the reactive doublebond of the monomer. Hexamethyldisiloxane is used here an internalstandard (i.e., internal reference) 42 and is seen at about 0 ppm. Itwill be appreciated that other compounds may be employed as an internalstandard. In FIG. 3A, the NMR spectrogram was measured on a firstaliquot taken from a specimen initiated with sodium benzoate at a molarratio of monomer to initiator of about 100:1. The first aliquot wastaken after the reaction had propagated for about 30 seconds at roomtemperature. The first aliquot was quenched with an acid to stop thepropagation reaction. FIG. 3B shows the NMR spectrogram from a secondaliquot taken from the same specimen after about 5 minutes of thepropagation reaction. As seen in FIG. 3B, the monomer is no longerdetectable as evidenced by a lack of the reactive double bond peak atabout 6.45 ppm 40.

The polymers according to the teachings herein preferably have a numberaverage molecular weight or a weight average molecular weight that isabout 700 g/mole or more, more preferably about 2,000 g/mole or more,even more preferably about 10,000 g/mole or more, and most preferablyabout 20,000 g/mole or more. The molecular weight of the polymer may besufficiently low so that the polymer may be easily processed. The numberaverage molecular weight or the weight average molecular weightpreferably is about 3,000,000 g/mole or less, more preferably about1,000,000 g/mole or less, even more preferably about 500,000 g/mole orless, and most preferably about 200,000 g/mole or less.

The resulting polymer may be a relatively low molecular weight polymerhaving a number average molecular weight of about 40,000 g/mole or less,about 30,000 g/mole or less, or about 20,000 g/mole or less. Theresulting polymer may be a relatively high molecular weight polymerhaving a number average molecular weight of greater than 40,000 g/mole,about 60,000 g/mole or more, or about 100,000 g/mole or more.

The resulting polymer may be characterized by a polydispersity index ofabout 1.00 or more or about 1.05 or more. The resulting polymer may becharacterized by a polydispersity index of about 10 or less, preferablyabout 7 or less, more preferably about 4 or less, and most preferablyabout 2.3 or less. The resulting polymer may have a narrow molecularweight distribution such that the polydispersity index is about 1.9 orless, about 1.7 or less, about 1.5 or less, or about 1.3 or less.

Surprisingly, by employing an acid containing compound according to theteachings herein, it may be possible to reduce the polydispersity of apolymer (e.g., of a block polymer block) without a substantive reductionin the polymerization reaction rate. For example, the polydispersity ofthe ratio of the polymer prepared with the acid containing compound tothe polydispersity of a polymer prepared using the same method exceptwithout the use of the acid containing compound may be about 0.9 orless, about 0.8 or less, about 0.7 or less, or about 0.6 or less. Theratio of the time for converting 80% of the monomer to polymer for theprocess including the acid containing compound to the time forconverting 80% of the monomer to polymer in the identical process(except without the acid containing compound) preferably is about 5 orless, more preferably about 3 or less, even more preferably about 2 orless, and most preferably about 1.5 or less.

The molecular weight of the polymer may be measured using gel permeationchromatography (i.e., GPC), FIG. 4, illustrates a GPC curve for ahomopolymer prepared by polymerizing diethyl methylene malonate in anemulsion system with deionized water as the carrier liquid. Sodiumbenzoate is used as the activator for the anionic polymerization of themonomer. The molar ratio of monomer to the sodium benzoate activator isabout 100:1. The reaction was continued until about 100 percent of themonomer was converted to polymer. The GPC curve 58 of the resultinghomopolymer is shown in FIG. 4. This sample has a single peak whichdefines an area 50 for calculating the molecular weight characteristicsof the polymer (e.g., weight average molecular weight, peak molecularweight, number average molecular weight, z-average molecular weight, andpolydispsersity index). The GPC curve 58 shows the signal intensity(which correlates with concentration) as a function of the retentiontime in minutes. The calibration curve 54 is also shown in FIG. 4. Thecalibration curve shows the retention time for a series of PMMAstandards of known molecular weight. The low limit 56 for measuring themolecular weight based on these standards is about 200 daltons. Thepolymer of diethyl methylene malonate characterized in FIG. 4 has anumber average molecular weight of about 747, a weight average molecularweight of about 943, and a polydispersity index (i.e., Mw/Mn) of about1.26.

The emulsion micelle or polymer particle size and/or particle sizedistribution (e.g., after the completion of polymerization) may becontrolled based on process considerations, based on product controlconsiderations, based on application requirements, or any combinationthereof. For example, there may be a need for emulsion particles havinga unimodal particle size distribution, a multi-modal particle sizedistribution (e.g., a bimodal distribution), a narrow particle sizedistribution, a broad particle size distribution, or any combinationthereof. In some situations, it may be desirable to prepare generallylarge emulsion particles (i.e., having a number average radius of about1 μm or more or a number average diameter of about 2 μm or more,preferably having a number average radius of about 2 μm or more). Inother situations, it may be desirable to prepare generally smallemulsion particles (i.e., having an average radius of less than about 1μm, preferably about 0.7 μm or less). The emulsion particles preferablyhave a number average diameter of about 10 mm or less, about 2 mm orless, about 1 mm or less, about 300 μm or less, about 100 μm or less, orabout 50 μm or less. The emulsion particles preferably have a numberaverage diameter of about 0.01 μm or more, about 0.02 μm or more, about0.05 μm or more, about 0.10 μm or more.

Control of the particle size may be accomplished by any known means. Forexample, the particle size may be controlled by the amount and/or typeof surfactant, the type of any agitation, the amount of agitation, orany combination thereof. By way of example, mechanical agitation, bystirring or otherwise, may be varied (e.g., by varying the mixing speed)to obtain a desired particle size. In general, the particle size maydecrease with increasing mixing speed. However, as the mixing speedincreases, a plateau may be reached where further increases in mixingspeed does not affect the particle size. In general, it may be possibleto obtain smaller particle size (e.g., generally small emulsion particlesize) using other means of agitation, such as sonication. When usingsonication, the frequency preferably is about 0.2 kHz or more, morepreferably about 1 kHz or more, even more preferably about 5 kHz ormore, and most preferably about 20 kHz or more. Typically the frequencyis about 1000 kHz or less, about 500 kHz or less, about 200 kHz or less,or about 100 kHz or less.

It will be appreciated that particle size may be also controlled afterthe completion of polymerization. For example, two or more emulsionshaving different number average particle size and/or different particlesize distributions may be combined to achieve a desired resulting numberaverage particle size and/or a desired resulting particle sizedistribution. As used herein, the particle size distribution may becharacterized by any known method. For example, the particle sizedistribution may be characterized by the standard deviation of theparticle size, the modality (i.e., number of peaks) of a particle sizedistribution curve, or a ratio of the average particle size to thenumber average particle size. The ratio of the standard deviation of theparticle size to the number average particle size preferably is about0.80 or less, more preferably about 0.60 or less, even more preferablyabout 0.45 or less, and most preferably about 0.30 or less.

The emulsion polymer according to the teachings herein may becharacterized as an elastomer. For example, the emulsion polymer may besubstantially free of a melting temperature and substantially free of aglass transition temperature of about 15° C. or more.

The emulsion polymer according to the teaching herein may becharacterized as a thermoplastic having a melting temperature and/or aglass transition temperature of about 15° C. or more, about 50° C. ormore, about 80° C. or more, about 100° C. or more, or about 120° C. ormore. Polymers having a high glass transition temperature include thosehaving hydrocarbonyl groups that provide steric hindrance that reducethe mobility of polymer molecules in the melt state. The meltingtemperature and/or the glass transition temperature of the thermoplasticmay be about 250° C. or less, about 200° C. or less, or about 150° C. orless.

The emulsion polymer according to the teachings herein may becharacterized as a block copolymer including at least one block having aglass transition temperature or melting temperature of about 15° C. ormore (e.g., about 50° C. or more, about 80° C. or more, or about 100° C.or more) and at least one different block having no melting temperatureabove 15° C. and having a glass transition temperature of less than 15°C. (e.g., about 10° C. or less, about 0° C. or less, or about −20° C. orless). In one aspect, a block copolymer may be prepared with blocks thatare not miscible so that the resulting block copolymer has multiplephases at room temperature. As such, the block copolymer may have afirst glass transition temperature corresponding to the first polymerblock and a second glass transition temperature corresponding to thesecond polymer block. It will be appreciated that the glass transitiontemperature of the blocks may be tailored based on the monomer ormonomers used in the particular block and/or based on end effects (whichincludes the effect of the number of monomer units in the block). Forpurposes of illustration, a polymer block consisting essentially of, orconsisting entirely of: (1) diethyl methylene malonate homopolymer isexpected to have a glass transition temperature of about 25° C. to about45° C. (preferably about 35° C.), (2) fenchyl methyl methylene malonateis expected to have a glass transition temperature of about 125° C. toabout 155° C. (preferably about 143° C.), (3) methyl methoxyethylmethylene malonate is expected to have a glass transition temperature ofabout −15° C. to about +10° C. (preferably about 0° C.), (4) hexylmethyl methylene malonate is expected to have a glass transitiontemperature of about −45° C. to about −20° C. (preferably about −34°C.), (5) dibutyl methylene malonate is expected to have a glasstransition temperature of about −55° C. to about −35° C. (preferablyabout −44° C.). It may be possible to prepare a block copolymer havingmultiple glass transition temperatures, such as a first glass transitiontemperature characteristic of a first polymer block and a second glasstransition temperature characteristic of a second polymer block. In someblock copolymers, a single glass transition is observed indicating thata single phase is formed, indicating that the two polymer blocks havesubstantially the same glass transition temperature (e.g., a differenceof about 20° C. or less, about 10° C. or less, or both).

The emulsion polymer according to the teachings herein may be acharacterized as a random copolymer and/or having a polymer block thatis a random copolymer. The random copolymer may include a primarymonomer (e.g., present at a concentration of about 50 mole percent ormore) and a secondary monomer randomly distributed through the polymerchain and having a concentration of less than 50 mole percent. Theproperties of the random copolymer will generally differ from theproperties of a homopolymer consisting entirely of the primary monomer.For example, as the amount of the secondary monomer is increased fromabout 0.5 mole percent to about 49.5 mole percent, the glass transitiontemperature of the random copolymer may shift from a glass transitiontemperature characteristic of the primary monomer towards a glasstransition temperature characteristic of the secondary monomer. Whenprepared as a random copolymer, the polymer typically has a single glasstransition temperature (e.g., even when a mixture of a homopolymer ofthe primary monomer and a homopolymer of the secondary monomer, at thesame concentration, exhibits multiple glass transition temperatures).

The homopolymer of the primary monomer may be a semicrystalline polymer.Typically, when a secondary monomer is added in preparing a randomcopolymer, the secondary monomer will partially inhibit the ability ofthe primary monomer to crystallize, resulting in a random copolymerhaving different properties from the homopolymer such as a lowercrystallinity, a lower flexural modulus, a lower melting temperature, orany combination thereof. For example, the selection of the secondarymonomer and/or the amount of the secondary monomer in the randomcopolymer may be selected so that the random copolymer has a meltingtemperature that is reduced (i.e., relative to the homopolymer of theprimary monomer) by about 5° C. or more, by about 10° C. or more, byabout 15° C. or more, or by about 20° C. or more. The selection of thesecondary monomer and/or the amount of the secondary monomer in therandom copolymer may be selected so that the random copolymer has acrystallintity that is reduced (i.e., relative to the homopolymer of theprimary monomer) by about 10% or more, by about 20% or more, by 40% ormore, or by about 60% or more.

The resulting polymer may be a block copolymer including at least afirst polymer block and a second polymer block different from the firstpolymer block. The first polymer block and the second polymer block maydiffer with respect to one or any combination of the followingproperties: peak melting temperature, final melting temperature,crystallinity, glass transition temperature, flexural modulus, tensilemodulus, elongation at failure, gas barrier properties, or adhesionproperties. For example, the first polymer block and the second polymerblock may have melting temperatures (peak melting temperatures and/orfinal melting temperatures) differing by about 10° C. or more, about 20°C. or more, about 30° C. or more, or about 50° C. or more. It will beappreciated that one polymer block may have a melting temperature andthe other polymer block may be free of crystalline polymer so that thereis no measurable melting temperature. The first polymer block and thesecond polymer block may have glass transition temperatures differing byabout 10° C. or more, about 20° C. or more, about 30° C. or more, orabout 40° C. or more. The first polymer block and the second polymerblock may have crystallinities that differ by about 10% or more, about15% or more, about 20% or more, about 25% or more, or about 30% or more.The first polymer block and the second polymer block may have moduli(e.g., flex modulus, tensile modulus, or both) having a ratio of about1.5 or more, about 2 or more, about 4 or more, about 8 or more, or about15 or more. The first polymer block and the second polymer block mayhave a ratio of elongation at failure and/or a ratio of tensile strengthof about 2 or more, about 3 or more, about 4 or more, or about 6 ormore.

The degree of blockiness (i.e, the blockiness index, or BI) in a randomcopolymer may be calculated by the ratio of the concentration of diadfractions of a first monomer (e.g., a primary monomer that is a1,1-disubstituted alkene compound) added to the second monomer f(M1−M2)plus the diad fractions of the second monomer added to the first monomerf(M2−M1) to the theoretical concentration of diad fractions for astatistical random copolymer 2 X_(M1) (1−X_(M1)), where X_(M1) is themolar fraction of first monomer:

BI=(f(M1−M2)+f(M2-M1))/(2X _(M1)(1−X _(M2)))

By definition a true statistically random copolymer has a BI of one(1.0). Blocky random copolymers will have a lower concentration of M1−M2and M2−M1 diad fractions, and BI will be less than 1.0. Block copolymerswill have very low concentrations of M1−M2 and M2−M1 diad fractions andBI will be much less than 1 and approach zero. On the other end,alternating copolymers having X_(M1)≧0.5 will have BI=1+(1/X_(M1)). Theconcentration of the diad fractions and X_(M1) may be measured using ¹³CNMR spectroscopy, using analogous peak assignments and techniquesdescribed by Yi-Jun Huange et al. in “Random Copolymers of PropyleneOxide and Ethylene Oxide Prepared by Double Metal Cyanide ComplexCatalyst”, Chinese Journal of Polymer Science, 20:5, 2002, pages453-459, incorporated herein by reference in its entirety.

Preferred random copolymers have a BI of about 0.70 or more, morepreferably about 0.75 or more, even more preferably about 0.80 or more,even more preferably about 0.85 or more, even more preferably about 0.90or more, and most preferably about 0.95 or more. Preferred randomcopolymers have a BI preferably less than about 1+(0.8/x_(M1)), morepreferably less than about 1+(0.5/x_(M1)), even more preferably lessthan about 1+(0.25/x_(M1)), and most preferably less than about1+(0.10/x_(M1)) where x_(M1) is the molar fraction of primary monomer inthe copolymer and x_(M1) is at least 0.5.

The resulting emulsion polymer may be employed in a polymericcomposition including one or more additives, such as antioxidants, heatstabilizers, light stabilizers, process stabilizers, lubricants,antiblocking agents, antistatic agent, anti-fogging agents, solvents,plasticizers, fillers, antistatic agents, coupling agents (e.g., for thefillers), crosslinking agents, nucleating agent, anti-blocking agent,defoaming agents, pigments, colorant, flame retardant additives, flowaid, lubricant, slip agent and other processing aids known to thepolymer compounding art. Suitable flame retardants may include halogencontaining flame retardants and halogen free flame retardants.

Polymeric compositions may comprise one or more other fillers, such as afiller particle (e.g., fibers, powders, beads, flakes, granules, and thelike). The filler particle may be a fiber (e.g., having an aspect ratioof the longest direction to each perpendicular direction that is greaterthan 10). The filler particle may be a particle that is not a fiber(e.g., having an aspect ratio of the longest direction to aperpendicular direction that is less than 10, less than 8, or less than5). The filler may be formed of an organic material and/or an inorganicmaterial. Examples of organic fillers include fillers derived frombiomass and fillers derived from polymers. Inorganic fillers include,nonmetallic materials, metallic materials, and semiconductor material.For example, the filler particle may include alumina silicate, aluminumhydroxide, alumina, silicon oxide, barium sulfate, bentonite, boronnitride, calcium carbonate (e.g., activated calcium carbonate, lightcalcium carbonate, or heavy calcium carbonate), calcium hydroxide,calcium silicate, calcium sulfate, carbon black, clay, cotton flock,cork powder, diatomaceous earth, dolomite, ebonite powder, glass,graphite, hydrotalcite, iron oxide, iron metallic particles, kaolin,mica, magnesium carbonate, magnesium hydroxide, magnesium oxide,phosphide, pumice, pyrophyllite, sericite, silica, silicon carbide,talc, titanium oxide, wollastonite, zeolite, zirconium oxide, or anycombination thereof. The filler particles may be present at aconcentration of about 0.1 weight percent or more, about 1 weightpercent or more, about 5 weight percent or more, or about 10 weighpercent or more. The filler particles may be present at a concentrationof about 70 weight percent or less, about 50 weight percent or less,about 35 weight percent or less, or about 25 weigh percent or less. Thefiller particles preferably have one, two, or three dimensions that areabout 1 mm or less, about 0.3 mm or less, about 0.1 mm, about 50 μm orless, about 10 μm or less. The filler particles preferably have one,two, or three dimensions that are about 0.1 μm or more, about 0.3 μm ormore, or about 1 μm or more.

The polymeric compositions according to the teachings herein may includea plasticizer for adjusting the properties of the final polymer for thedesired use. The plasticizer may be added prior to, during, or afterpolymerization. For example, in certain embodiments, a suitableplasticizer can be included with the 1,1-disubstituted alkene monomer.Generally, suitable plasticizers can include plasticizers used to modifythe rheological properties of adhesive systems including, for example,straight and branched chain alkyl-phthalates such as diisononylphthalate, dioctyl phthalate, and dibutyl phthalate, as well aspartially hydrogenated terpene, trioctyl phosphate, epoxy plasticizers,toluene-sulfamide, chloroparaffins, adipic acid esters, sebacates suchas dimethyl sebacate, castor oil, xylene, 1-methyl-2-pyrrolidione andtoluene. Commercial plasticizers such as HB-40 manufactured by SolutiaInc. (St. Louis, Mo.) can also be suitable.

The process may include one or more steps of monitoring or otherwisemeasuring the conversion rate of the monomer to polymer. Theconcentration of the remaining monomer may be determined for exampleusing NMR spectroscopy. For example, quantitative NMR spectroscopy maybe employed to measure the concentration of alkylene groups (e.g.,1-ethylene groups) remaining in the emulsion system.

The emulsion polymer of the current teaching may be mixed with one ormore additional polymers for preparing a polymeric composition. Theconcentration of the emulsion polymer in the polymeric composition maybe about 1 weight percent or more, about 5 weight percent or more, about10 weight percent or more, about 20 weight percent or more, or about 50weight percent or more, based on the total weight of the polymers in thepolymeric composition. The emulsion polymer may be present in thepolymeric composition at a concentration of about 100 weight percent orless, about 95 weight percent or less, or about 90 weight percent orless, or about 60 weight percent or less, based on the total weight ofthe polymers in the polymeric composition.

The process may include one or more steps of removing some or all of thecarrier liquid from the emulsion polymer. The process of removing thecarrier liquid may use heat, reduced pressure or both for separating thepolymer from the carrier liquid. The process of removing the carrierliquid may include a step of filtering and/or a step of adding one ormore additional liquids to the emulsion.

The process may include one or more steps of terminating (i.e.,quenching) the anionic polymerization reaction. For example,polymerization can be quenched by contacting the emulsion with ananionic polymerization terminator. In some embodiments the anionicpolymerization terminator is an acid. In some embodiments it isdesirable to utilize a sufficient amount of the acid to render thepolymerization mixture (e.g., the emulsion) slightly acidic, preferablyhaving a pH of less than 7, more preferably less than 6. Exemplaryanionic polymerization terminators include, for example, mineral acidssuch as methanesulfonic acid, sulfuric acid, and phosphoric acid andcarboxylic acids such as acetic acid and trifluoroacetic acid.

The polymers and polymer compositions according to the teachings herein(e.g., after removing some or all of the carrier liquid) may have one ormore rheological properties (e.g., melt index, melt flow rate,viscosity, melt strength, and the like) suitable for processing thepolymer with known polymer processing equipment. For example, thepolymer or polymer composition including 1,1-disubstituted alkenecompounds may be processed using extrusion, co-extrusion, injectionmolding, insert molding, co-injection molding, calendaring (e.g., usingtwo or more rolls), blow molding, compression molding, thermoforming,rolling, spray coating. For example, the polymeric material (i.e., thepolymer or the polymer composition) may be fed through a processingapparatus having a screw and a barrel assembly wherein the polymericmaterial is conveyed along the screw at a temperature at which thepolymeric material is at least partially in a liquid state (e.g., aboveany glass transition temperature and above any melting temperature).

The polymers according to the teachings herein preferably adhere to oneor more of the following substrates: aluminum, steel, glass, silicon, orwood. For example, when separating two substrates having the polymerplaced between the substrates, the separation of the substrates mayresult in cohesive failure of the polymer, where some polymer remains onthe surfaces of the substrates.

The polymers according to the teachings herein may be employed inextruded, blow molded, injection molded, thermoformed, or compressionmolded articles. The polymers may be employed as an adhesive. Forexample, the polymers may be employed in a pressure sensitive adhesivecomposition. The polymers may be employed as a coating, such as aprotective coating. The polymer may be employed as a primer layer over asubstrate.

Melting temperatures and glass transition temperatures are measuredusing differential scanning calorimetry on a sample of about 0.5-1.0 mg.The sample is heated at a rate of about 10° C./min and then cooled at arate of about 20° C./min.

The molecular weight is determined using gel permeation chromatography.GPC samples are prepared by first quenching with trifluoroacetic acidand then drying the polymer to remove the carrier liquid (e.g., thewater). The dried polymer is dissolved in tetrahydrofuran (THF). About25 uL of the dissolved polymer solution is injected into the THF eluenthaving a flow rate of 1 mL/min. Two columns with 5 micron, highlycrosslinked polystyrene/divinylbenzene matrix particles are employed.These columns are designed to measure molecular weights of linearpolymers from 200 to 2,000,000. The column pressure is about 65 bar andthe column temperature is about 35° C. The elution time is 30 minutes.The column is calibrated using PMMA standards. As such, the units formolecular weight are relative based on the standard PMMA equivalentmolecular weights.

Monomer conversion is calculated using quantitative NMR. A 300 MHz NMRis employed. Any residual polymerization reaction of the emulsionpolymerization specimen is quenched prior to NMR analysis by addingtrifluoroacetic acid. The preferred solvent is DMSO-d6 as it is a polaraprotic solvent. When the solvent is added to the emulsion, the aqueousand non-aqueous phases become miscible. Acetic acid is added as aninternal standard and is suitable for these monomer compositions. Thedouble bond intensity at about 6.45 ppm is measured to determine theconcentration of unconverted monomer. This double bond is a singlet forsymmetrical monomers such as diethyl methylene malonate and dibutylmethylene malonate, and it is a doublet for asymmetrical monomers suchas hexyl methyl methylene malonate. Four NMR scans are run on eachspecimen with a 20 second delay between scans.

Examples

Example 1 is a polymer prepared by emulsion polymerization of diethylmethylene malonate at a temperature of about 23° C. A 100 ml PYREX®beaker is charged with about 20.955 g of deionized water and 0.045 g ofa surfactant, 4-dodecylbenzenesulfonic acid (DBSA). The water andsurfactant are mixed for about 10 minutes at 500 rpm. About 1 mL of a 1weight percent sodium benzoate solution in deionized water is added tothe mixture and mixing is continued for about 5 minutes. About 9 g ofdiethyl methylene malonate is then added dropwise while mixing at about1500 rpm. The sodium benzoate acts as an activator for thepolymerization. The molar ratio of monomer to activator is about 500:1.The polymerization method is anionic in nature and occurs in the monomermicelles dispersed in the deionized water. The final ratio of water tomonomer/polymer is about 70:30. The reaction is monitored usingquantitative NMR by removing an aliquot of the emulsion, quenching withtrifluoroactetic acid, mixing with DMSO-d6, and adding acetic acid asthe internal standard. After 99.9% or more of the monomer is convertedto polymer as determined by the quantitative NMR, about 100 ppm oftrifluoroacetic acid is added to quench the reaction. The polymer isthen characterized using gel permeation chromatography. The GPC iscalibrated using PMMA standards and is used to measure the molecularweight distribution of the polymer. Example 1 has a number averagemolecular weight of about 15,579, a weight average molecular weight ofabout 21,010, and a polydispersity index of about 1.36.

Examples 2 and 3 are prepared using the same method as Example 1, exceptthe concentration of the sodium benzoate is changed so that the molarratio of monomer to activator is about 1000:1 and about 100:1,respectively. The conversion of monomer to polymer is greater than about99.9 percent.

Examples 4 through 6 are prepared using the same method as Example 1,except the molar ratio of monomer to activator is 100:1 and theactivator is 1,1,3,3-tetramethylguanidine, pyridine, and sodiumsilicate, respectively. The conversion of monomer to polymer is greaterthan about 99.9 percent.

The molecular weight distributions of Examples 1 through 6 are shown inthe Table 1.

TABLE 1 Example Example Example Example Example Example 1 2 3 4 5 6Activator Sodium Benzoate X X X 1,1,3,3-Tetramethylguanidine X PyridineX Sodium Silicate X Ratio of monomer to activator 500:1 1000:1 100:1100:1 100:1 100:1 Polymer Properties Conversion of monomer topolymer >99.9% >99.9% >99.9% >99.9% >99.9% >99.9% Number averagemolecular weight 15,579 55,031 747 1,173 991 1,289 Weight averagemolecular weight 21,010 71,022 943 1,582 1,334 1,724 PolydispersityIndex 1.36 1.29 1.26 1.26 1.35 1.34

Example 7 is prepared by emulsion polymerization of diethyl methylenemalonate at a temperature of about 23° C. About 20.7 g of deionizedwater and a surfactant are mixed in a 100 mL PYREX® beaker for about 10minutes at about 500 rpm. The surfactant is2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylate (commercially availableas SURFYNOL® 485) and the amount of the surfactant is about 0.3 g. About9 g of the monomer, diethyl methyl malonate, is added rapidly (e.g., inless than about 10 seconds) while mixing at about 500 rpm, formingmicelles of the monomer in the water. About 0.503 mL of a 1 weightpercent sodium benzoate solution is then added dropwise while mixing at1500-2000 rpm. The sodium benzoate is the activator for the reaction andthe ratio of monomer to activator is about 1000:1. The polymerizationreaction is continued for about one hour. The polymerization reaction isquenched by adding about 500 ppm (i.e., about 0.05 weight percent) oftrifluoroacetic acid to the emulsion. The conversion of monomer topolymer is greater than 99.9 percent as determined by quantitative NMR.

Example 8 is prepared according to the method of Example 7, except thesurfactant is 0.3 g of a tri-block copolymer of poly(ethyleneglycol)-block-poly(propylene glycol)-block-(polyethylene glycol).

Example 9 is prepared according to the method of Example 7, except thesurfactant is 0.3 g of CARBOWET® 138. This surfactant includes alkylalcohol, polyethylene glycol, and ethoxylated C9-11 alcohols.

Example 10 is prepared according to the method of Example 7, except thesurfactant is 0.3 g of sorbitan monopalmmitate. This surfactant is asoft solid at room temperature. The reaction temperature is raised toabout 46° C. to improve the dispersion of the surfactant during thepolymerization process.

Example 11 is prepared according to the method of Example 7, except thesurfactant is 0.3 g of IGEPAL® CO-720. This surfactant includespolyoxyethylene (12) nonylphenyl ether, branched.

Example 12 is prepared according to the method of Example 7, except thesurfactant is 0.3 g of poly(ethylene glycol) sorbitol hexaoleate.

In examples 7-12, the conversion of monomer to polymer was about 100percent.

Examples 13-17 are prepared according to the method of Example 7, exceptthe molar ratio of the monomer to the activator (sodium benzoate) is100:1, 200:1, 500:1, 8000:1, and 16000:1, respectively. Each of theresulting polymers has a conversion of monomer to polymer of about 100percent. The molecular weight characterization of Example 7 and 13-17are listed in Table 2.

TABLE 2 Example Example Example Example Example Example 7 13 14 15 16 17Activator Sodium Benzoate X X X X X X Surfactant SURFYNOL ® 485 X X X XX X Ratio of monomer to activator 1000:1 100:1 200:1 500:1 8000:116000:1 Polymer Properties Conversion of monomer to polymer ≈onve ≈onve≈onve ≈onve ≈onve ≈onve Number average molecular weight 4,161 9,4427,290 6,939 3104 1226 Weight average molecular weight 13,535 18,60517,782 18,038 5411 2237 Polydispersity Index 3.25 2.5 2.43 2.60 1.941.82

Freeze/thaw stability is evaluated by first measuring the initialviscosity of the polymer specimen. The polymer specimen is then placedin a chamber at a temperature of about −24° C. for about 17 hours, andthen to a room temperature of about 22° C. for about 7 hours. This 24hour cycle is repeated 5 times. The viscosity of the specimen ismeasured after being at room temperature for about 7 hours. The specimenis also observed for any signs of settling, gelation, or coagulationwhich would indicate an instable emulsion system. Conversely, noobserved signs of settling, gelation, or coagulation indicates a stableemulsion system.

Example FTSS-1 is a sample of poly (diethyl methylene malonate) (i.e.,poly(DEMM)) having a number average molecular weight of about 995 andprepared by emulsion polymerization. The initial viscosity of ExampleFTSS-1 is about 10-22 cPs. After 5 freeze/thaw cycles, the specimenstill has a viscosity of about 10-22 cPs. During the 5 cycles, there isno indication of settling, gelation, or coagulation.

Example FTSS-2 is a sample of poly (dibutyl methylene malonate) (i.e.,poly(DBMM)) having a number average molecular weight of about 2121 andprepared by emulsion polymerization. The initial viscosity of ExampleFTSS-2 is about 13-24 cPs. After 5 freeze/thaw cycles, the specimenstill has a viscosity of about 13-24 cPs. During the 5 cycles, there isno indication of settling, gelation, or coagulation.

Example FTSS-3 is a sample of poly (hexyl methyl methylene malonate)(i.e., poly(HMMM)) having a number average molecular weight of about5018 and prepared by emulsion polymerization. The initial viscosity ofExample FTSS-3 is about 15-25 cPs. After 5 freeze/thaw cycles, thespecimen still has a viscosity of about 15-25 cPs. During the 5 cycles,there is no indication of settling, gelation, or coagulation.

Example FTSS-4 is a sample of poly(DEMM) having a number averagemolecular weight of about 25,000 prepared by emulsion polymerization.The polymer is tested for freeze/thaw stability. After 5 freeze/thawcycles, Example FTSS-4 shows signs of settling, gelation andcoagulation, and does not flow.

Examples FTSS-5, FTSS-6, FTSS-7, FTSS-8, and FTSS-9 are samples ofpoly(DEMM) are prepared having number average molecular weight of 25,345through 498,003, as shown in Table 3. About 0.05 weight percent ofhydroxyethyl cellulose stabilizer is added to each of the polymersamples. After 5 freeze/thaw cycles, there is no evidence of settling,gelation, or coagulation, and the final viscosity is substantiallyunchanged from the initial viscosity.

TABLE 3 Example Example Example Example Example FTSS-5 FTSS-6 FTSS-7FTSS-8 FTSS-9 Number Average Molecular Weight 25,345 50,989 125,129209,039 498,003 Initial Viscosity, cPs  9 to 22 10 to 24 10 to 20 10 to24 15 to 25 Viscosity after 5 freeze/thaw cycles 11 to 25 12 to 24 10 to20 12 to 24 12 to 23 Settling/Gelation/Coagulation after None None NoneNone None 5 freeze/thaw cycles

Examples E-1, E-2, E-3, E-4, E-5, E-6, E-7, and E-8 are prepared bypolymerizing diethyl methyl malonate monomer using different mixtures ofsurfactants. The emulsion polymerization is performed at about 23° C.using a weight ratio of deionized water to monomer/polymer of about70:30. The surfactant is 2,4,7,9-tetramethyl-5-decyne-4,7-diolethoxylate (commercially available as SURFYNOL® 485), or4-dodecylbenzenesulfonic acid (DBSA), or a mixture of the twosurfactants. The surfactant and amount of surfactant for each Example isshown in Table 4. The activator is sodium benzoate and is added at amonomer to activator ratio of about 100:1. The monomer is added whilemixing the deionized water, surfactant, and activator at about 1500 rpm.The monomer is added in total within about 5 seconds. The approximatetimes for 95% and 99% conversion of monomer to polymer (as measuredusing quantitative NMR spectroscopy) is listed in Table 4. The reactionis continued for 4 hours. The final conversion is also listed in Table4. About 500 ppm of trifluoroacetic acid is added to the emulsion toquench the reaction. The molecular weight of the resulting polymer isthen measured using GPC. The weight average molecular weight, numberaverage molecular weight and polydispersity index for each polymer isgiven in Table 4. Although addition of DBSA slows down the reactionrate, addition of small amounts of DBSA (e.g., less than about 1500 ppm)results in a high polymerization reaction rates and polymers having anarrow molecular weight distribution.

TABLE 4 Example Example Example Example Example Example Example ExampleE-1 E-2 E-3 E-4 E-5 E-6 E-7 E-8 Surfynol 485 2 wt. % 2 wt. % 2 wt. % 2wt. % 2 wt. % 2 wt. % 2 wt. % 0 wt. % DBSA, ppm 0 500 1000 2000 30004000 5000 5000 Number average 6939 14109 2756 931 721 687 764 15579molecular weight Weight average 18038 17258 4104 1150 908 904 950 21010molecular weight Polydispersity Index 2.60 1.22 1.49 1.24 1.26 1.32 1.241.35 Monomer Conversion, 99.98 99.99 99.99 99.32 98.83 89.73 89.03 16.92% (after 4 hours) Time for 95% <1 ≈4 ≈6 ≈250 ≈300 >480 >480 >480conversion (min) Time for 99% ≈7 ≈7 ≈8 ≈400 >480 >480 >480 >480conversion (min)

Homopolymer Example H-1 is prepared via emulsion polymerization usingdiethyl methyl malonate. The emulsion is prepared by adding asurfactant, deionized water, and diethyl methyl malonate monomer to areaction vessel and stirring the mixture to form an emulsion of themonomer in the water. The polymerization reaction is conducted at about23° C. The weight ratio of the deionized water to the monomer/polymer isabout 70:30. The surfactant is 2,4,7,9-tetramethyl-5-decyne-4,7-diolethoxylate (commercially available as SURFYNOL® 485) and the amount ofthe surfactant is about 2 weight percent, based on the total weight ofthe emulsion. The reaction is initiated by adding sodium benzoate to thereaction vessel. The molar ratio of diethyl methylene malonate monomerto sodium benzoate is about 200:1. The reaction time is about 10 minutesand the conversion of the monomer to polymer is greater than 99.9%. Thereaction is quenched by adding about 500 ppm of trifluoroacetic acid tothe emulsion. The resulting polymer isolated and then dissolved in asolvent of dichloromethane or tetrahydrofuran. The solution is thenprecipitated at −25° C. about 4 times the volume of methanol. Theprecipitate is then further washed with a mixture of hexane and methanol(1:1 ratio by weight) at −25° C. The precipitate is filtered orotherwise separated from the liquids. The washing step removedessentially all of the surfactant and other non-reaction materials orimpurities. The recovered polymer has a weight average molecular weightgreater than 50,000 and a glass transition temperature of about 35° C.

Homopolymer Example H-2 is prepared using the same procedure as forExample H-1, except the diethyl methyl malonate monomer is replaced withfenchyl methyl methylene malonate monomer and the initiator is sodiumsilicate at a molar ratio of monomer to activator of about 200:1. Therecovered polymer has a weight average molecular weight greater than50,000 and a glass transition temperature of about 143° C.

Homopolymer Example H-3 is prepared using the same procedure as forExample H-1, except the diethyl methyl malonate monomer is replaced withmethylmethoxy ethyl methylene malonate monomer and the initiator issodium silicate at a molar ratio of monomer to activator of about 200:1.The recovered polymer has a weight average molecular weight greater than50,000 and a glass transition temperature of about 0° C.

Homopolymer Example H-4 is prepared using the same procedure as forExample H-1, except the diethyl methyl malonate monomer is replaced withhexyl methyl methylene malonate monomer and the initiator is sodiumsilicate at a molar ratio of monomer to activator of about 200:1. Therecovered polymer has a weight average molecular weight greater than50,000 and a glass transition temperature of about −34° C.

Homopolymer Example H-5 is prepared using the same procedure as forExample H-1, except the diethyl methyl malonate monomer is replaced withdibutyl methylene malonate monomer and the surfactant is sodium silicateat a molar ratio of monomer to activator of about 200:1. The recoveredpolymer has a weight average molecular weight greater than 50,000 and aglass transition temperature of about −44° C.

Homopolymer Example H-6 is prepared using the same procedure as forExample H-1, except the molar ratio of the diethyl methylene malonatemonomer to the sodium benzoate activator is about 100:1. In preparingExample H-6, the solution is agitated using a mixing speed of about 400rpm. The mixing time is about 1 hour. The resulting emulsion is measuredusing dynamic light scattering. The polymer particles have a refractiveindex of about 1.81. The number average particle size is about 28.6 μmwith a standard deviation of about 7.6 μm. Homopolymer Example H-7 isprepared using the same procedure as for Example H-6, except the mixingspeed was increased to about 1500 rpm. The resulting polymer particleshave a refractive index of about 1.81, an average particle size of about6.44 μm with a standard deviation of about 3.31 μm. Homopolymer ExampleH-8 is prepared using the same procedure as for Example H-6, except theagitation was achieved using sonication at a frequency of about 40 kHz.The resulting polymer particles have a refractive index of about 1.81,an average particle size of about 0.48 μm with a standard deviation ofabout 0.09 μm. The homopolymer results for H-1 through H-6 aresummarized in Table 5.

TABLE 5 Example Example Example Example Example H-1 H-2 H-3 H-4 H-5Monomer DEMM FMMM MMOEMM HMMM DBMM Type of polymer homoplymer homoplymerhomoplymer homoplymer homoplymer Weightaverage >50,000 >50,000 >50,000 >50,000 >50,000 molecular weight, MwGlass Transition 35 143 0 −34 −44 Temp., ° C. Monomerconversion >99.9% >99.9% >99.9% >99.9% >99.9%

Example M-1 is a mixture of two homopolymers, homopolymer Example H-1and homopolymer Example H-2 are dissolved together in dichloromethanesolvent at a weight ratio of the two homopolymers of 1:1. The polymermixture is then precipitated from solution by adding methanol (at about−25° C.) at a volume of about 4 times the volume of the solvent. Theprecipitated polymer is further washed with a 1:1 mixture (by weight) ofmethanol and hexane (at about −25° C.). The resulting polymer mixturehas two glass transition temperatures at about 45° C. and at about 137°C.

Example M-2 is a mixture of two homopolymers, homopolymer Example H-1and homopolymer Example H-3. The polymer mixture is prepared using thesame method as described above for Example M-1, except homopolymerExample H-2 is replaced by homopolymer Example H-3. The resultingpolymer mixture has two glass transition temperatures at about 28° C.and at about 12° C.

Example M-3 is a mixture of two homopolymers, homopolymer Example H-1and homopolymer Example H-4. The polymer mixture is prepared using thesame method as described above for Example M-1, except homopolymerExample H-2 is replaced by homopolymer Example H-4. The resultingpolymer mixture has two glass transition temperatures at about 25° C.and at about −25° C.

Example M-4 is a mixture of two homopolymers, homopolymer Example H-1and homopolymer Example H-3. The polymer mixture is prepared using thesame method as described above for Example M-1, except homopolymerExample H-2 is replaced by homopolymer Example H-5. The resultingpolymer mixture has a single glass transition temperature at about −5°C.

Example M-5 is a mixture of two homopolymers, homopolymer Example H-2and homopolymer Example H-3. The polymer mixture is prepared using thesame method as described above for Example M-1, except homopolymerExample H-1 is replaced by homopolymer Example H-2, and homopolymerExample H-2 is replaced by homopolymer Example H-3. The resultingpolymer mixture has two glass transition temperatures at about 131° C.and at about 10° C.

Example M-6 is a mixture of two homopolymers, homopolymer Example H-2and homopolymer Example H-4. The polymer mixture is prepared using thesame method as described above for Example M-1, except homopolymerExample H-1 is replaced by homopolymer Example H-2, and homopolymerExample H-2 is replaced by homopolymer Example H-4. The resultingpolymer mixture has two glass transition temperatures at about 132° C.and at about −14° C.

Example M-7 is a mixture of two homopolymers, homopolymer Example H-2and homopolymer Example H-5. The polymer mixture is prepared using thesame method as described above for Example M-1, except homopolymerExample H-1 is replaced by homopolymer Example H-2, and homopolymerExample H-2 is replaced by homopolymer Example H-5. The resultingpolymer mixture has two glass transition temperatures at about 129° C.and at about −33° C.

Example M-8 is a mixture of two homopolymers, homopolymer Example H-3and homopolymer Example H-4. The polymer mixture is prepared using thesame method as described above for Example M-1, except homopolymerExample H-1 is replaced by homopolymer Example H-3, and homopolymerExample H-2 is replaced by homopolymer Example H-4. The resultingpolymer mixture has two glass transition temperatures at about −7° C.and at about −25° C.

Example M-9 is a mixture of two homopolymers, homopolymer Example H-3and homopolymer Example H-5. The polymer mixture is prepared using thesame method as described above for Example M-1, except homopolymerExample H-1 is replaced by homopolymer Example H-3, and homopolymerExample H-2 is replaced by homopolymer Example H-5. The resultingpolymer mixture has two glass transition temperatures at about −9° C.and at about −36° C.

Example M-10 is a mixture of two homopolymers, homopolymer Example H-3and homopolymer Example H-5. The polymer mixture is prepared using thesame method as described above for Example M-1, except homopolymerExample H-1 is replaced by homopolymer Example H-4, and homopolymerExample H-2 is replaced by homopolymer Example H-5. The resultingpolymer mixture has a single glass transition temperature at about −37°C.

Examples R-1 through R-10 are random copolymer prepared according to themethod of Example H-1 homopolymer, except the monomer of diethyl methylmalonate is replaced with a 1:1 weight ratio of monomer 1 and monomer 2,as listed in Table 5. The resulting polymers are random copolymershaving a weight average molecular weight of 50,000 or more, and having aconversion of monomer to polymer of greater than 99.9 weight percent.Each of the random copolymers has a single glass transition temperatureas shown in the Table 6.

Example B-1 is a block copolymer prepared by sequentially polymerizing afirst polymer block, a second polymer block, and a third polymer block.The first polymer block is prepared as described above for homopolymerExample H-1, except the amount of the monomer is reduced to aboutone-third of the monomer employed in Example H-1. After preparing thefirst polymer block, a sample of the polymer (Example B-1 stage 1) isremoved, quenched with about 500 ppm of trifluoroacetic acid,precipitated, and washed for analysis, as described above. The remainingpolymer is further polymerized by adding a second monomer (fenchylmethyl methylene malonate) to the emulsion to form a second polymerblock consisting essentially of the second monomer. The amount of thesecond monomer is about one-third of the total monomer used in ExampleH-1. After preparing the second polymer block, a sample of the diblockpolymer (Example B-1 stage 2) is removed, quenched with about 500 ppmtrifluoroacetic acid, precipitated, and washed for analysis. Theremaining polymer is further polymerized by adding an additional amountof the first monomer into the emulsion to polymerize a third polymerblock consisting essentially of the first monomer. The amount of thethird monomer is about one-third of the monomer employed in Example H-1.The resulting tri-block copolymer (Example B-1 stage 3) is quenched withabout 500 ppm of trifluoroacetic acid, precipitated, and washed asdescribed above for hompolymer Example H-1.

TABLE 6 Glass Example Transition Number Monomer 1 Monomer 2 Temp, ° C.Example R-1 Diethyl methylene malonate fenchyl methyl methylene malonate88 Example R-2 Diethyl methylene malonate methylmethoxy ethyl methylene17 malonate Example R-3 Diethyl methylene malonate hexyl methylmethylene malonate 1 Example R-4 Diethyl methylene malonate dibutylmethylene malonate −4 Example R-5 fenchyl methyl methylene methylmethoxyethyl methylene 72 malonate malonate Example R-6 fenchyl methylmethylene hexyl methyl methylene malonate 55 malonate Example R-7fenchyl methyl methylene dibutyl methylene malonate 50 malonate ExampleR-8 methylmethoxy ethyl methylene hexyl methyl methylene malonate −16malonate Example R-9 methylmethoxy ethyl methylene dibutyl methylenemalonate −22 malonate Example R-10 hexyl methyl methylene malonatedibutyl methylene malonate −38

Examples B-2, B-3, and B-4 are block copolymers prepared according tothe method described above for Example B-1, except the second monomer offenchyl methyl methylene malonate is replaced with methylmethoxy ethylmethylene malonate, hexyl methyl methylene malonate, and dibutylmethylene malonate, respectively.

The properties of Examples B-1, B-2, B-3, and B-4 at the end of each ofthe three stages (single block, diblock, and triblock) are listed inTable 7.

TABLE 7 Example B-1 Example B-2 Example B-3 Example B-4 After stage 1(single block) Monomer DEMM DEMM DEMM DEMM Conversion, wt.% >99.9 >99.9 >99.9 >99.9 Mn 16167 16191 16103 16093 PolydispersityIndex 1.3 1.3 1.3 1.3 Glass Transition Temp, ° C. 34 35 35 34 Afterstage 2 (diblock) Monomer FMMM MMOEMM HMMM DBMM Conversion, wt.% >99.8 >99.9 >99.9 >99.8 Mn 29384 31903 30789 28263 PolydispersityIndex 2.1 1.9 1.8 2.0 Glass Transition Temp, ° C. 48 and 132  8 and 27−26 and 23 −8 After stage 3 (triblock) Monomer DEMM DEMM DEMM DEMMConversion, wt. % >99.8 >99.8 >99.9 >99.7 Mn 44102 45093 44387 42561Polydispersity Index 2.9 2.4 2.2 2.6 Glass Transition Temp, ° C. 38 and125 15 and 33  −9 and 32 10

A pressure sensitive adhesive emulsion composition is prepared by mixingabout 67.98 parts deionized water, about 0.03 parts4-dodecylbenzenesulfonic acid, and about 2.00 parts ethoxylated2,4,7,9-tetramethyl-5-decyne-4,7-diol at about 700 rpm. A 10% solutionof sodium silicate activator in deionized water is added at about 0.42parts (for a monomer to activator molar ratio of about 200:1) and mixedat about 1,000 rpm. About 27.75 parts hexyl methyl methylene malonatemonomer is added in bulk and mixing is continued at about 1,000 rpm.After the polymerization reaction is completed, the emulsion is appliedto a steel plate and the water is removed by evaporation. The resultingpolymer is a pressure sensitive adhesive and possess representative tackas a result of the polymer. When a crosslinker is added and the PSAmaterial is adhered to steel panel, substantially no polymer istransferred off of the steel panel when a second substrate is appliedand removed. The PSA material has good stability after 5 freeze/thawcycles.

REFERENCE SIGNS FROM DRAWINGS

-   -   10 Emulsion system    -   12 Continuous liquid phase    -   14 Dispersed phase/Emulsion micelle    -   16 Surfactant/Surfactant layer    -   18 Interior of micelle    -   20 Outer surface of micelle/Outer surface of surfactant layer    -   22 Inner surface of surfactant layer    -   24 Interior of micelle    -   26 Monomer/Polymer    -   28 Carrier liquid    -   30 Illustrative steps included in an emulsion polymerization        process    -   32 Step of combining a carrier liquid, surfactant and monomer        with agitation to prepare a multi-phase system    -   34 Step of adding an activator to begin a polymerization        reaction    -   36 Step of propagating the polymer by an anionic polymerization        reaction    -   37 Optional step of adding one or more monomers and/or        continuously feeding one or more monomers (e.g., after        substantially all of the previously added monomer has been        consumed).    -   38 Optional step of quenching the polymerization reaction    -   40 About 6.45 ppm on the NMR spectrograph (corresponding to the        reactive double bond peak of diethyl methylene malonate)    -   42 About 0 ppm on the NMR spectrograph-internal reference    -   50 GPC peak and area of calculation    -   52 Weight Average Molecular Weight (Mw)    -   54 Calibration curve (molecular weight v. retention time) based        on PMMA standards    -   56 Lowest molecular weight calibration (200 daltons)    -   58 GPC Curve

What is claimed is:
 1. An emulsion comprising: i) 30 weight percent ormore of a continuous phase including a carrier fluid including water;ii) a dispersed phase including a polymer and having a surfactant layerin contact with the polymer and with the carrier fluid; wherein thepolymer is present in an amount of about 10 weight percent or more,includes one or more monomers including one or more 1,1-disubstitutedalkene compounds, and has a number average molecular weight of about 700g/mole or more.
 2. The emulsion of claim 1, wherein the polymer has apolydispersity index of about 1.7 or less.
 3. The emulsion of claim 1,wherein the polymer has a number average molecular weight of about 2,000g/mole to about 1,000,000 g/mole.
 4. The emulsion of claim 1, whereinthe discrete phase includes micelles having a number average radius ofabout 0.10 μm to about 300 μm.
 5. The emulsion of claim 4, wherein theconcentration of the polymer is about 20 weight percent or more.
 6. Theemulsion of claim 5, wherein the carrier liquid consists essentially ofwater, and i) the concentration of the carrier liquid is sufficientlyhigh so that the emulsion is capable of flowing; or ii) the ratio of thezero shear viscosity of the emulsion to the zero shear viscosity of thepolymer at 25° C. is about 0.2 or less.
 7. The emulsion of claim 6,wherein the carrier liquid is present in an amount of about 65 weightpercent or less, based on the total weight of the emulsion.
 8. Theemulsion of claim 7, wherein the polymer is formed by a polymerizationactivated by one or more monomers activator includes an ionic metalamide, an hydroxide, a cyanide, a phosphine, an alkoxide, an amine, anorganometallic compound, or a metal benzoate; wherein the molar ratio ofthe one or more monomers to the monomer activators is greater than about50:1.
 9. The emulsion of claim 7, wherein the one or more1,1-disubstituted alkenes includes imethyl propyl methylene malonate,dihexyl methylene malonate, di-isopropyl methylene malonate, butylmethyl methylene malonate, ethoxyethyl ethyl methylene malonate,methoxyethyl methyl methylene malonate, hexyl methyl methylene malonate,dipentyl methylene malonate, ethyl pentyl methylene malonate, methylpentyl methylene malonate, ethyl ethylmethoxy methylene malonate,ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate,dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxyethyl methylene malonate, dimethyl methylene malonate, di-N-propylmethylene malonate, ethyl hexyl methylene malonate, methyl fenchylmethylene malonate, ethyl fenchyl methylene malonate, 2 phenylpropylethyl methylene malonate, 3 phenylpropyl ethyl methylene malonate, ordimethoxy ethyl methylene malonate.
 10. The emulsion of claim 9, whereinthe polymer includes a first 1,1-disubstituted alkene and a second1,1-disubstituted alkene.
 11. The emulsion of claim 10, wherein theresulting polymer includes a first polymer block including about 10weight percent or more of a first 1,1-disubstituted alkene; and a secondpolymer block including less than 10 weight percent of the first1,1-disubstituted alkene.
 12. The emulsion of claim 11, wherein thepolymer is a random copolymer including the 1,1-disubstituted alkene anda second monomer.
 13. The emulsion of claim 7, wherein the one or moremonomers includes: i) a first 1,1-disubstituted alkenes including methylpropyl methylene malonate, dihexyl methylene malonate, di-isopropylmethylene malonate, butyl methyl methylene malonate, ethoxyethyl ethylmethylene malonate, methoxyethyl methyl methylene malonate, hexyl methylmethylene malonate, dipentyl methylene malonate, ethyl pentyl methylenemalonate, methyl pentyl methylene malonate, ethyl ethylmethoxy methylenemalonate, ethoxyethyl methyl methylene malonate, butyl ethyl methylenemalonate, dibutyl methylene malonate, diethyl methylene malonate (DEMM),diethoxy ethyl methylene malonate, dimethyl methylene malonate,di-N-propyl methylene malonate, ethyl hexyl methylene malonate, methylfenchyl methylene malonate, ethyl fenchyl methylene malonate, 2phenylpropyl ethyl methylene malonate, 3 phenylpropyl ethyl methylenemalonate, or dimethoxy ethyl methylene malonate; and ii) a different1,1-disubstituted alkene including methyl propyl methylene malonate,dihexyl methylene malonate, di-isopropyl methylene malonate, butylmethyl methylene malonate, ethoxyethyl ethyl methylene malonate,methoxyethyl methyl methylene malonate, hexyl methyl methylene malonate,dipentyl methylene malonate, ethyl pentyl methylene malonate, methylpentyl methylene malonate, ethyl ethylmethoxy methylene malonate,ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate,dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxyethyl methylene malonate, dimethyl methylene malonate, di-N-propylmethylene malonate, ethyl hexyl methylene malonate, methyl fenchylmethylene malonate, ethyl fenchyl methylene malonate, 2 phenylpropylethyl methylene malonate, 3 phenylpropyl ethyl methylene malonate, ordimethoxy ethyl methylene malonate;
 14. The emulsion of claim 1, whereinthe resulting polymer includes a first polymer block including about 10weight percent or more of a first 1,1-disubstituted alkene; and a secondpolymer block including less than 10 weight percent of the first1,1-disubstituted alkene.
 15. The emulsion of claim 1, wherein thepolymer is a block copolymer including a first block having a glasstransition temperature of 15° C. or more, and a second polymer blockhaving a glass transition temperature of less than 15° C.
 16. Theemulsion of claim 1, wherein the wherein the 1,1-disubstituted alkene isa compound having a hydrocarbyl group bonded to each of the two carbonylgroups through a direct bond or through an oxygen atom.
 17. The emulsionof claim 16, wherein the polymer is a random copolymer including the1,1-disubstituted alkene and a second monomer.
 18. The process of claim17, wherein the polymer is a block copolymer including a first blockhaving a first glass transition temperature and a second block having asecond glass transition temperature, wherein the first and second glasstransition temperatures differ by about 20° C. or more.
 19. An adhesiveincluding the emulsion of claim 1, wherein the adhesive is a water-basedadhesive and the carrier liquid consists essentially of water.
 20. Theadhesive of claim 19, wherein the adhesive is a pressure sensitiveadhesive.
 21. A coating including the emulsion of claim 1, wherein thecoating is a water-based coating and the carrier liquid consistsessentially of water.